Heating An Organic-Rich Rock Formation In Situ To Produce Products With Improved Properties

ABSTRACT

A method of producing hydrocarbon fluids with improved hydrocarbon compound properties from a subsurface organic-rich rock formation, such as an oil shale formation, is provided. The method may include the step of heating the organic-rich rock formation in situ. In accordance with the method, the heating of the organic-rich rock formation may pyrolyze at least a portion of the formation hydrocarbons, for example kerogen, to create hydrocarbon fluids. Thereafter, the hydrocarbon fluids may be produced from the formation. Hydrocarbon fluids with improved hydrocarbon compound properties are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of co-pending U.S. application Ser. No.11/973,898 filed Oct. 10, 2007 titled, Heating An Organic-Rich RockFormation in Situ To Produce Products With Improved Properties, herebyincorporated by reference in its entirety, which claims the benefit ofU.S. Provisional application 60/997,654, titled “Products with ImprovedAromatic Hydrocarbon Properties Produced by In Situ Heating of anOrganic-Rich Rock Formation”, docket No. 2007EM267, which was filed onOct. 4, 2007, U.S. Provisional application 60/997,650, titled “Heatingan Organic-Rich Rock Formation In Situ to Produce Products with ImprovedAromatic Hydrocarbon Properties”, docket No. 2007EM266, which was filedon Oct. 4, 2007, U.S. Provisional application 60/997,646, titled“Products with Improved Branched Hydrocarbon Properties Produced by InSitu Heating of an Organic-Rich Rock Formation”, docket No. 2007EM269,which was filed on Oct. 4, 2007, U.S. Provisional application60/997,645, titled “Heating an Organic-Rich Rock Formation In Situ toProduce Products with Improved Branched Hydrocarbon Properties”, docketNo. 2007EM268, which was filed on Oct. 4, 2007, U.S. Provisionalapplication 60/997,648, titled “Products with Improved CyclicHydrocarbon Properties Produced by In Situ Heating of an Organic-RichRock Formation”, docket No. 2007EM271, which was filed on Oct. 4, 2007,U.S. Provisional application 60/997,653, titled “Heating an Organic-RichRock Formation In Situ to Produce Products with Improved CyclicHydrocarbon Properties”, docket No. 2007EM270, which was filed on Oct.4, 2007, U.S. Provisional application 60/997,649, titled “Products withIdentifying Compound Marker Properties Produced by In Situ Heating of anOrganic-Rich Rock Formation”, docket No. 2007EM272, which was filed onOct. 4, 2007, U.S. Provisional application 60/851,432 which was filed onOct. 13, 2006, U.S. Provisional application 60/851,534 which was filedon Oct. 13, 2006, U.S. Provisional application 60/851,535 which wasfiled on Oct. 13, 2006, U.S. Provisional application 60/851,819 whichwas filed on Oct. 13, 2006, U.S. Provisional application 60/851,786which was filed on Oct. 13, 2006, and U.S. Provisional application60/851,820 which was filed on Oct. 13, 2006. The above-referencedprovisional applications are incorporated herein in their entirety byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the field of hydrocarbon recovery fromsubsurface formations. More specifically, the present invention relatesto in situ recovery of hydrocarbon fluids from organic-rich rockformations, including, for example, oil shale formations, coalformations and tar sands formations.

2. Background of the Invention

Certain geological formations are known to contain an organic matterknown as “kerogen.” Kerogen is a solid, carbonaceous material. Whenkerogen is imbedded in rock formations, the mixture is referred to asoil shale. This is true whether or not the mineral is, in fact,technically shale, that is, a rock formed from compacted clay.

Kerogen is subject to decomposing upon exposure to heat over a period oftime. Upon heating, kerogen molecularly decomposes to produce oil, gas,and carbonaceous coke. Small amounts of water may also be generated. Theoil, gas and water fluids are mobile within the rock matrix, while thecarbonaceous coke remains essentially immobile.

Oil shale formations are found in various areas world-wide, includingthe United States. Oil shale formations tend to reside at relativelyshallow depths. In the United States, oil shale is most notably found inWyoming, Colorado, and Utah. These formations are often characterized bylimited permeability. Some consider oil shale formations to behydrocarbon deposits which have not yet experienced the years of heatand pressure thought to be required to create conventional oil and gasreserves.

The decomposition rate of kerogen to produce mobile hydrocarbons istemperature dependent. Temperatures generally in excess of 270° C. (518°F.) over the course of many months may be required for substantialconversion. At higher temperatures substantial conversion may occurwithin shorter times. When kerogen is heated, chemical reactions breakthe larger molecules forming the solid kerogen into smaller molecules ofoil and gas. The thermal conversion process is referred to as pyrolysisor retorting.

Attempts have been made for many years to extract oil from oil shaleformations. Near-surface oil shales have been mined and retorted at thesurface for over a century. In 1862, James Young began processingScottish oil shales. The industry lasted for about 100 years. Commercialoil shale retorting through surface mining has been conducted in othercountries as well such as Australia, Brazil, China, Estonia, France,Russia, South Africa, Spain, and Sweden. However, the practice has beenmostly discontinued in recent years because it proved to be uneconomicalor because of environmental constraints on spent shale disposal. (See T.F. Yen, and G. V. Chilingarian, “Oil Shale,” Amsterdam, Elsevier, p.292, the entire disclosure of which is incorporated herein byreference.) Further, surface retorting requires mining of the oil shale,which limits application to very shallow formations.

In the United States, the existence of oil shale deposits innorthwestern Colorado has been known since the early 1900's. Whileresearch projects have been conducted in this area from time to time, noserious commercial development has been undertaken. Most research on oilshale production has been carried out in the latter half of the 1900's.The majority of this research was on shale oil geology, geochemistry,and retorting in surface facilities.

In 1947, U.S. Pat. No. 2,732,195 issued to Ljungstrom. That patent,entitled “Method of Treating Oil Shale and Recovery of Oil and OtherMineral Products Therefrom,” proposed the application of heat at hightemperatures to the oil shale formation in situ to distill and producehydrocarbons. The '195 Ljungstrom patent is incorporated herein byreference.

Ljungstrom coined the phrase “heat supply channels” to describe boreholes drilled into the formation. The bore holes received an electricalheat conductor which transferred heat to the surrounding oil shale.Thus, the heat supply channels served as heat injection wells. Theelectrical heating elements in the heat injection wells were placedwithin sand or cement or other heat-conductive material to permit theheat injection well to transmit heat into the surrounding oil shalewhile preventing the inflow of fluid. According to Ljungstrom, the“aggregate” was heated to between 500° and 1,000° C. in someapplications.

Along with the heat injection wells, fluid producing wells were alsocompleted in near proximity to the heat injection wells. As kerogen waspyrolyzed upon heat conduction into the rock matrix, the resulting oiland gas would be recovered through the adjacent production wells.

Ljungstrom applied his approach of thermal conduction from heatedwellbores through the Swedish Shale Oil Company. A full scale plant wasdeveloped that operated from 1944 into the 1950's. (See G. Salamonsson,“The Ljungstrom In Situ Method for Shale-Oil Recovery,” 2^(nd) Oil Shaleand Cannel Coal Conference, v. 2, Glasgow, Scotland, Institute ofPetroleum, London, p. 260-280 (1951), the entire disclosure of which isincorporated herein by reference.)

Additional in situ methods have been proposed. These methods generallyinvolve the injection of heat and/or solvent into a subsurface oilshale. Heat may be in the form of heated methane (see U.S. Pat. No.3,241,611 to J. L. Dougan), flue gas, or superheated steam (see U.S.Pat. No. 3,400,762 to D. W. Peacock). Heat may also be in the form ofelectric resistive heating, dielectric heating, radio frequency (RF)heating (U.S. Pat. No. 4,140,180, assigned to the ITT Research Institutein Chicago, Ill.) or oxidant injection to support in situ combustion. Insome instances, artificial permeability has been created in the matrixto aid the movement of pyrolyzed fluids. Permeability generation methodsinclude mining, rubblization, hydraulic fracturing (see U.S. Pat. No.3,468,376 to M. L. Slusser and U.S. Pat. No. 3,513,914 to J. V. Vogel),explosive fracturing (see U.S. Pat. No. 1,422,204 to W. W. Hoover, etal.), heat fracturing (see U.S. Pat. No. 3,284,281 to R. W. Thomas), andsteam fracturing (see U.S. Pat. No. 2,952,450 to H. Purre).

In 1989, U.S. Pat. No. 4,886,118 issued to Shell Oil Company, the entiredisclosure of which is incorporated herein by reference. That patent,entitled “Conductively Heating a Subterranean Oil Shale to CreatePermeability and Subsequently Produce Oil,” declared that “[c]ontrary tothe implications of . . . prior teachings and beliefs . . . thepresently described conductive heating process is economically feasiblefor use even in a substantially impermeable subterranean oil shale.”(col. 6, ln. 50-54). Despite this declaration, it is noted that few, ifany, commercial in situ shale oil operations have occurred other thanLjungstrom's application. The '118 patent proposed controlling the rateof heat conduction within the rock surrounding each heat injection wellto provide a uniform heat front.

Additional history behind oil shale retorting and shale oil recovery canbe found in co-owned patent U.S. Pat. No. 7,331,385 entitled “Methods ofTreating a Subterranean Formation to Convert Organic Matter intoProducible Hydrocarbons,” and in patent U.S. Patent No. 7,441,603entitled “Hydrocarbon Recovery from Impermeable Oil Shales.” TheBackground and technical disclosures of these two patent publicationsare incorporated herein by reference.

A need exists for improved processes for the production of shale oil. Inaddition, a need exists for improved methods of producing shale oil withimproved properties.

SUMMARY OF THE INVENTION

In one embodiment, the invention includes a hydrocarbon fluid producedthrough in situ pyrolysis of oil shale within an oil shale formationwhere the hydrocarbon fluid comprises a condensable hydrocarbon portionand the condensable hydrocarbon portion has one or more of a n-C6 tobenzene weight ratio less than 35.0, a n-C7 to toluene weight ratio lessthan 7.0, a n-C8 to ethylbenzene weight ratio less than 16.0, a n-C8 toortho-xylene weight ratio less than 7.0, a n-C8 to meta-xylene weightratio less than 1.9, a n-C9 to 1-ethyl-3-methylbenzene weight ratio lessthan 8.2, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.4,a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.7, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, a n-C10 totetralin weight ratio less than 25.0, a n-C12 to 2-methylnaphthaleneweight ratio less than 4.9, and a n-C12 to 1-methylnaphthalene weightratio less than 6.9.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation where the hydrocarbon fluid comprises a condensablehydrocarbon portion and the condensable hydrocarbon portion has one ormore of a n-C6 to benzene weight ratio less than 24.0, a n-C7 to tolueneweight ratio less than 6.6, a n-C8 to ethylbenzene weight ratio lessthan 15.0, a n-C8 to ortho-xylene weight ratio less than 6.6, a n-C8 tometa-xylene weight ratio less than 1.8, a n-C9 to1-ethyl-3-methylbenzene weight ratio less than 7.9, a n-C9 to1-ethyl-4-methylbenzene weight ratio less than 4.3, a n-C9 to1,2,4-trimethylbenzene weight ratio less than 2.6, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 13.1, a n-C10 totetralin weight ratio less than 23.7, a n-C12 to 2-methylnaphthaleneweight ratio less than 5.0, and a n-C12 to 1-methylnaphthalene weightratio less than 6.8.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation where the hydrocarbon fluid comprises a condensablehydrocarbon portion and the condensable hydrocarbon portion has one ormore of a n-C6 to benzene weight ratio less than 13.4, a n-C7 to tolueneweight ratio less than 5.1, a n-C8 to ethylbenzene weight ratio lessthan 12.3, a n-C8 to ortho-xylene weight ratio less than 5.3, a n-C8 tometa-xylene weight ratio less than 1.5, a n-C9 to1-ethyl-3-methylbenzene weight ratio less than 5.9, a n-C9 to1-ethyl-4-methylbenzene weight ratio less than 3.8, a n-C9 to1,2,4-trimethylbenzene weight ratio less than 2.2, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 12.2, a n-C10 totetralin weight ratio less than 23.4, a n-C12 to 2-methylnaphthaleneweight ratio less than 4.0, and a n-C12 to 1-methylnaphthalene weightratio less than 6.1.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluids from an organic-rich rock formation. The method mayinclude heating in situ a section of an organic-rich rock formationcontaining formation hydrocarbons, where the section of an organic-richrock formation has a lithostatic stress greater than 200 psi, pyrolyzingat least a portion of the formation hydrocarbons thereby forming ahydrocarbon fluid, and producing the hydrocarbon fluid from theorganic-rich rock formation. The produced hydrocarbon fluid may includea condensable hydrocarbon portion, where the condensable hydrocarbonportion has one or more of a n-C6 to benzene weight ratio less than35.0, a n-C7 to toluene weight ratio less than 7.0, a n-C8 toethylbenzene weight ratio less than 16.0, a n-C8 to ortho-xylene weightratio less than 7.0, a n-C8 to meta-xylene weight ratio less than 1.9, an-C9 to 1-ethyl-3-methylbenzene weight ratio less than 8.2, a n-C9 to1-ethyl-4-methylbenzene weight ratio less than 4.4, a n-C9 to1,2,4-trimethylbenzene weight ratio less than 2.7, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, a n-C10 totetralin weight ratio less than 25.0, a n-C12 to 2-methylnaphthaleneweight ratio less than 4.9, and a n-C12 to 1-methylnaphthalene weightratio less than 6.9.

In one embodiment, the invention includes a hydrocarbon fluid producedthrough in situ pyrolysis of oil shale within an oil shale formationwhere the hydrocarbon fluid comprises a condensable hydrocarbon portionand the condensable hydrocarbon portion has one or more of a n-C9 toIP-9 weight ratio greater than 2.4, a n-C10 to IP-10 weight ratiogreater than 1.4, a n-C11 to IP-11 weight ratio greater than 1.0, an-C13 to IP-13 weight ratio greater than 1.1, a n-C14 to IP-14 weightratio greater than 1.1, a n-C15 to IP-15 weight ratio greater than 1.0,a n-C16 to IP-16 weight ratio greater than 0.8, a n-C18 to IP-18 weightratio greater than 1.0, and a n-C19 to pristane weight ratio greaterthan 1.6.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation where the hydrocarbon fluid comprises a condensablehydrocarbon portion and the condensable hydrocarbon portion has one ormore of a n-C9 to IP-9 weight ratio greater than 2.5, a n-C10 to IP-10weight ratio greater than 1.5, a n-C11 to IP-11 weight ratio greaterthan 1.1, a n-C13 to IP-13 weight ratio greater than 1.2, a n-C14 toIP-14 weight ratio greater than 1.2, a n-C15 to IP-15 weight ratiogreater than 1.1, a n-C16 to IP-16 weight ratio greater than 0.9, an-C18 to IP-18 weight ratio greater than 1.1, and a n-C19 to pristaneweight ratio greater than 1.8.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation where the hydrocarbon fluid comprises a condensablehydrocarbon portion and the condensable hydrocarbon portion has one ormore of a n-C9 to IP-9 weight ratio greater than 2.6, a n-C10 to IP-10weight ratio greater than 1.6, a n-C11 to IP-11 weight ratio greaterthan 1.2, a n-C13 to IP-13 weight ratio greater than 1.3, a n-C14 toIP-14 weight ratio greater than 1.4, a n-C15 to IP-15 weight ratiogreater than 1.4, a n-C16 to IP-16 weight ratio greater than 1.2, an-C18 to IP-18 weight ratio greater than 1.5, and a n-C19 to pristaneweight ratio greater than 2.4.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluids from an organic-rich rock formation. The method mayinclude heating in situ a section of an organic-rich rock formationcontaining formation hydrocarbons, where the section of an organic-richrock formation has a lithostatic stress greater than 200 psi, pyrolyzingat least a portion of the formation hydrocarbons thereby forming ahydrocarbon fluid, and producing the hydrocarbon fluid from theorganic-rich rock formation. The produced hydrocarbon fluid may includea condensable hydrocarbon portion, where the condensable hydrocarbonportion has one or more of a n-C9 to IP-9 weight ratio greater than 2.4,a n-C10 to IP-10 weight ratio greater than 1.4, a n-C11 to IP-11 weightratio greater than 1.0, a n-C13 to IP-13 weight ratio greater than 1.1,a n-C14 to IP-14 weight ratio greater than 1.1, a n-C15 to IP-15 weightratio greater than 1.0, a n-C16 to IP-16 weight ratio greater than 0.8,a n-C18 to IP-18 weight ratio greater than 1.0, and a n-C19 to pristaneweight ratio greater than 1.6.

In one embodiment, the invention includes a hydrocarbon fluid producedthrough in situ pyrolysis of oil shale within an oil shale formationwhere the hydrocarbon fluid comprises a condensable hydrocarbon portionand the condensable hydrocarbon portion has one or more of a n-C7 to cis1,3-dimethyl cyclopentane weight ratio less than 13.1, a n-C7 to trans1,3-dimethyl cyclopentane weight ratio less than 14.9, a n-C7 to trans1,2-dimethyl cyclopentane weight ratio less than 7.0, a n-C7 to methylcyclohexane weight ratio less than 5.2, a n-C7 to ethyl cyclopentaneweight ratio less than 11.3, a n-C8 to 1,1-dimethyl cyclohexane weightratio less than 16.0, a n-C8 to trans 1,2-dimethyl cyclohexane weightratio less than 17.5, and a n-C8 to ethyl cyclohexane weight ratio lessthan 12.3.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation where the hydrocarbon fluid comprises a condensablehydrocarbon portion and the condensable hydrocarbon portion has one ormore of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than12.7, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than14.7, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than6.6, a n-C7 to methyl cyclohexane weight ratio less than 5.0, a n-C7 toethyl cyclopentane weight ratio less than 10.9, a n-C8 to 1,1-dimethylcyclohexane weight ratio less than 15.4, a n-C8 to trans 1,2-dimethylcyclohexane weight ratio less than 16.5, and a n-C8 to ethyl cyclohexaneweight ratio less than 12.0.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation where the hydrocarbon fluid comprises a condensablehydrocarbon portion and the condensable hydrocarbon portion has one ormore of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than10.3, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than11.6, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than5.9, a n-C7 to methyl cyclohexane weight ratio less than 4.1, a n-C7 toethyl cyclopentane weight ratio less than 9.5, a n-C8 to 1,1-dimethylcyclohexane weight ratio less than 13.9, a n-C8 to trans 1,2-dimethylcyclohexane weight ratio less than 12.3, and a n-C8 to ethyl cyclohexaneweight ratio less than 10.3.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluids from an organic-rich rock formation. The method mayinclude heating in situ a section of an organic-rich rock formationcontaining formation hydrocarbons, where the section of an organic-richrock formation has a lithostatic stress greater than 200 psi, pyrolyzingat least a portion of the formation hydrocarbons thereby forming ahydrocarbon fluid, and producing the hydrocarbon fluid from theorganic-rich rock formation. The produced hydrocarbon fluid may includea condensable hydrocarbon portion, where the condensable hydrocarbonportion has one or more of a n-C7 to cis 1,3-dimethyl cyclopentaneweight ratio less than 13.1, a n-C7 to trans 1,3-dimethyl cyclopentaneweight ratio less than 14.9, a n-C7 to trans 1,2-dimethyl cyclopentaneweight ratio less than 7.0, a n-C7 to methyl cyclohexane weight ratioless than 5.2, a n-C7 to ethyl cyclopentane weight ratio less than 11.3,a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 16.0, a n-C8to trans 1,2-dimethyl cyclohexane weight ratio less than 17.5, and an-C8 to ethyl cyclohexane weight ratio less than 12.3.

In one embodiment, the invention includes a hydrocarbon fluid producedthrough in situ pyrolysis of oil shale within an oil shale formation.The hydrocarbon fluid including a condensable hydrocarbon portion. Thecondensable hydrocarbon portion having one or more of a total C9 tototal C20 weight ratio between 2.5 and 6.0, a total C10 to total C20weight ratio between 2.8 and 7.3, a total C11 to total C20 weight ratiobetween 2.6 and 6.5, a total C12 to total C20 weight ratio between 2.6and 6.4 and a total C13 to total C20 weight ratio between 3.2 and 8.0.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation. The hydrocarbon fluid including a condensable hydrocarbonportion. The condensable hydrocarbon portion having one or more of atotal C10 to total C25 weight ratio between 7.1 and 24.5, a total C11 tototal C25 weight ratio between 6.5 and 22.0, a total C12 to total C25weight ratio between 6.5 and 22.0, and a total C13 to total C25 weightratio between 8.0 and 27.0.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation. The hydrocarbon fluid including a condensable hydrocarbonportion. The condensable hydrocarbon portion having one or more of atotal C10 to total C29 weight ratio between 15.0 and 60.0, a total C11to total C29 weight ratio between 13.0 and 54.0, a total C12 to totalC29 weight ratio between 12.5 and 53.0, and a total C13 to total C29weight ratio between 16.0 and 65.0.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluid from an organic-rich rock formation. The methodincludes heating in situ a section of an organic-rich rock formationhaving a lithostatic stress greater than 200 psi. The method furtherincludes producing a hydrocarbon fluid from the organic-rich rockformation. The produced hydrocarbon fluid including a condensablehydrocarbon portion. The condensable hydrocarbon portion having one ormore of a total C7 to total C20 weight ratio greater than 0.8, a totalC8 to total C20 weight ratio greater than 1.7, a total C9 to total C20weight ratio greater than 2.5, a total C10 to total C20 weight ratiogreater than 2.8, a total C11 to total C20 weight ratio greater than2.3, a total C12 to total C20 weight ratio greater than 2.3, a total C13to total C20 weight ratio greater than 2.9, a total C14 to total C20weight ratio greater than 2.2, a total C15 to total C20 weight ratiogreater than 2.2, and a total C16 to total C20 weight ratio greater than1.6.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluid from an organic-rich rock formation. The methodincludes heating in situ a section of an organic-rich rock formationhaving a lithostatic stress greater than 200 psi. The method furtherincludes producing a hydrocarbon fluid from the organic-rich rockformation. The produced hydrocarbon fluid including a condensablehydrocarbon portion. The condensable hydrocarbon portion having one ormore of a total C7 to total C25 weight ratio greater than 2.0, a totalC8 to total C25 weight ratio greater than 4.5, a total C9 to total C25weight ratio greater than 6.5, a total C10 to total C25 weight ratiogreater than 7.5, a total C11 to total C25 weight ratio greater than6.5, a total C12 to total C25 weight ratio greater than 6.5, a total C13to total C25 weight ratio greater than 8.0, a total C14 to total C25weight ratio greater than 6.0, a total C15 to total C25 weight ratiogreater than 6.0, a total C16 to total C25 weight ratio greater than4.5, a total C17 to total C25 weight ratio greater than 4.8, and a totalC18 to total C25 weight ratio greater than 4.5.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluid from an organic-rich rock formation. The methodincludes heating in situ a section of an organic-rich rock formationhaving a lithostatic stress greater than 200 psi. The method furtherincludes producing a hydrocarbon fluid from the organic-rich rockformation. The produced hydrocarbon fluid including a condensablehydrocarbon portion. The condensable hydrocarbon portion having one ormore of a total C7 to total C29 weight ratio greater than 3.5, a totalC8 to total C29 weight ratio greater than 9.0, a total C9 to total C29weight ratio greater than 12.0, a total C10 to total C29 weight ratiogreater than 15.0, a total C11 to total C29 weight ratio greater than13.0, a total C12 to total C29 weight ratio greater than 12.5, a totalC13 to total C29 weight ratio greater than 16.0, a total C14 to totalC29 weight ratio greater than 12.0, a total C15 to total C29 weightratio greater than 12.0, a total C16 to total C29 weight ratio greaterthan 9.0, a total C17 to total C29 weight ratio greater than 10.0, atotal C18 to total C29 weight ratio greater than 8.8, a total C19 tototal C29 weight ratio greater than 7.0, a total C20 to total C29 weightratio greater than 6.0, a total C21 to total C29 weight ratio greaterthan 5.5, and a total C22 to total C29 weight ratio greater than 4.2.

In one embodiment, the invention includes a hydrocarbon fluid producedthrough in situ pyrolysis of oil shale within an oil shale formation.The hydrocarbon fluid including a condensable hydrocarbon portion. Thecondensable hydrocarbon portion having one or more of a normal-C7 tonormal-C20 weight ratio greater than 0.9, a normal-C8 to normal-C20weight ratio greater than 2.0, a normal-C9 to normal-C20 weight ratiogreater than 1.9, a normal-C10 to normal-C20 weight ratio greater than2.2, a normal-C11 to normal-C20 weight ratio greater than 1.9, anormal-C12 to normal-C20 weight ratio greater than 1.9, a normal-C13 tonormal-C20 weight ratio greater than 2.3, a normal-C14 to normal-C20weight ratio greater than 1.8, a normal-C15 to normal-C20 weight ratiogreater than 1.8, and normal-C16 to normal-C20 weight ratio greater than1.3.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation. The hydrocarbon fluid including a condensable hydrocarbonportion. The condensable hydrocarbon portion having one or more of anormal-C7 to normal-C25 weight ratio greater than 1.9, a normal-C8 tonormal-C25 weight ratio greater than 3.9, a normal-C9 to normal-C25weight ratio greater than 3.7, a normal-C10 to normal-C25 weight ratiogreater than 4.4, a normal-C11 to normal-C25 weight ratio greater than3.8, a normal-C12 to normal-C25 weight ratio greater than 3.7, anormal-C13 to normal-C25 weight ratio greater than 4.7, a normal-C14 tonormal-C25 weight ratio greater than 3.7, a normal-C15 to normal-C25weight ratio greater than 3.7, a normal-C16 to normal-C25 weight ratiogreater than 2.5, a normal-C17 to normal-C25 weight ratio greater than3.0, and a normal-C18 to normal-C25 weight ratio greater than 3.4.

Another embodiment of the invention includes a hydrocarbon fluidproduced through in situ pyrolysis of oil shale within an oil shaleformation. The hydrocarbon fluid including a condensable hydrocarbonportion. The condensable hydrocarbon portion having one or more of anormal-C7 to normal-C29 weight ratio greater than 18.0, a normal-C8 tonormal-C29 weight ratio greater than 16.0, a normal-C9 to normal-C29weight ratio greater than 14.0, a normal-C10 to normal-C29 weight ratiogreater than 14.0, a normal-C11 to normal-C29 weight ratio greater than13.0, a normal-C12 to normal-C29 weight ratio greater than 11.0, anormal-C13 to normal-C29 weight ratio greater than 10.0, a normal-C14 tonormal-C29 weight ratio greater than 9.0, a normal-C15 to normal-C29weight ratio greater than 8.0, a normal-C16 to normal-C29 weight ratiogreater than 8.0, a normal-C17 to normal-C29 weight ratio greater than6.0, a normal-C18 to normal-C29 weight ratio greater than 6.0, anormal-C19 to normal-C29 weight ratio greater than 5.0, a normal-C20 tonormal-C29 weight ratio greater than 4.0, a normal-C21 to normal-C29weight ratio greater than 3.6, and a normal-C22 to normal-C29 weightratio greater than 2.8.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluid from an organic-rich rock formation. The methodincludes heating in situ a section of an organic-rich rock formationhaving a lithostatic stress greater than 200 psi. The method furtherincludes producing a hydrocarbon fluid from the organic-rich rockformation. The produced hydrocarbon fluid including a condensablehydrocarbon portion. The condensable hydrocarbon portion having one ormore of a normal-C10 to normal-C20 weight ratio greater than 2.2, anormal-C11 to normal-C20 weight ratio greater than 1.9, a normal-C12 tonormal-C20 weight ratio greater than 1.9, a normal-C13 to normal-C20weight ratio greater than 2.3, a normal-C14 to normal-C20 weight ratiogreater than 1.8, a normal-C15 to normal-C20 weight ratio greater than1.8, and normal-C16 to normal-C20 weight ratio greater than 1.3.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluid from an organic-rich rock formation. The methodincludes heating in situ a section of an organic-rich rock formationhaving a lithostatic stress greater than 200 psi. The method furtherincludes producing a hydrocarbon fluid from the organic-rich rockformation. The produced hydrocarbon fluid including a condensablehydrocarbon portion. The condensable hydrocarbon portion having one ormore of a normal-C10 to normal-C25 weight ratio greater than 4.4, anormal-C11 to normal-C25 weight ratio greater than 3.8, a normal-C12 tonormal-C25 weight ratio greater than 3.7, a normal-C13 to normal-C25weight ratio greater than 4.7, a normal-C14 to normal-C25 weight ratiogreater than 3.7, a normal-C15 to normal-C25 weight ratio greater than3.7, a normal-C16 to normal-C25 weight ratio greater than 2.5, anormal-C17 to normal-C25 weight ratio greater than 3.0, and a normal-C18to normal-C25 weight ratio greater than 3.4.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluid from an organic-rich rock formation. The methodincludes heating in situ a section of an organic-rich rock formationhaving a lithostatic stress greater than 200 psi. The method furtherincludes producing a hydrocarbon fluid from the organic-rich rockformation. The produced hydrocarbon fluid including a condensablehydrocarbon portion. The condensable hydrocarbon portion having one ormore of a normal-C7 to normal-C29 weight ratio greater than 18.0, anormal-C8 to normal-C29 weight ratio greater than 16.0, a normal-C9 tonormal-C29 weight ratio greater than 14.0, a normal-C10 to normal-C29weight ratio greater than 14.0, a normal-C11 to normal-C29 weight ratiogreater than 13.0, a normal-C12 to normal-C29 weight ratio greater than11.0, a normal-C13 to normal-C29 weight ratio greater than 10.0, anormal-C14 to normal-C29 weight ratio greater than 9.0, a normal-C15 tonormal-C29 weight ratio greater than 8.0, a normal-C16 to normal-C29weight ratio greater than 8.0, a normal-C17 to normal-C29 weight ratiogreater than 6.0, a normal-C18 to normal-C29 weight ratio greater than6.0, a normal-C19 to normal-C29 weight ratio greater than 5.0, anormal-C20 to normal-C29 weight ratio greater than 4.0, a normal-C21 tonormal-C29 weight ratio greater than 3.6, and a normal-C22 to normal-C29weight ratio greater than 2.8.

In one embodiment, the invention includes a hydrocarbon fluid producedthrough in situ pyrolysis of oil shale within an oil shale formation.The hydrocarbon fluid including a condensable hydrocarbon portion. Thecondensable hydrocarbon portion having one or more of a normal-C10 tototal C10 weight ratio less than 0.31, a normal-C11 to total C11 weightratio less than 0.32, a normal-C12 to total C12 weight ratio less than0.29, a normal-C13 to total C13 weight ratio less than 0.28, anormal-C14 to total C14 weight ratio less than 0.31, a normal-C15 tototal C15 weight ratio less than 0.27, a normal-C16 to total C16 weightratio less than 0.31, a normal-C17 to total C17 weight ratio less than0.31, a normal-C18 to total C18 weight ratio less than 0.37, normal-C19to total C19 weight ratio less than 0.37, a normal-C20 to total C20weight ratio less than 0.37, a normal-C21 to total C21 weight ratio lessthan 0.37, a normal-C22 to total C22 weight ratio less than 0.38,normal-C23 to total C23 weight ratio less than 0.43, a normal-C24 tototal C24 weight ratio less than 0.48, and a normal-C25 to total C25weight ratio less than 0.53.

In one embodiment, the invention includes an in situ method of producinghydrocarbon fluid from an organic-rich rock formation. The methodincludes heating in situ a section of an organic-rich rock formationhaving a lithostatic stress greater than 200 psi. The method furtherincludes producing a hydrocarbon fluid from the organic-rich rockformation. The produced hydrocarbon fluid including a condensablehydrocarbon portion. The condensable hydrocarbon portion having one ormore of a normal-C10 to total C10 weight ratio less than 0.31, anormal-C11 to total C11 weight ratio less than 0.32, a normal-C12 tototal C12 weight ratio less than 0.29, a normal-C13 to total C13 weightratio less than 0.28, a normal-C14 to total C14 weight ratio less than0.31, a normal-C15 to total C15 weight ratio less than 0.27, anormal-C16 to total C16 weight ratio less than 0.31, a normal-C17 tototal C17 weight ratio less than 0.31, a normal-C18 to total C18 weightratio less than 0.37, normal-C19 to total C19 weight ratio less than0.37, a normal-C20 to total C20 weight ratio less than 0.37, anormal-C21 to total C21 weight ratio less than 0.37, a normal-C22 tototal C22 weight ratio less than 0.38, normal-C23 to total C23 weightratio less than 0.43, a normal-C24 to total C24 weight ratio less than0.48, and a normal-C25 to total C25 weight ratio less than 0.53.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the features of the present invention can bebetter understood, certain drawings, graphs and flow charts are appendedhereto. It is to be noted, however, that the drawings illustrate onlyselected embodiments of the inventions and are therefore not to beconsidered limiting of scope, for the inventions may admit to otherequally effective embodiments and applications.

FIG. 1 is a cross-sectional view of an illustrative subsurface area. Thesubsurface area includes an organic-rich rock matrix that defines asubsurface formation.

FIG. 2 is a flow chart demonstrating a general method of in situ thermalrecovery of oil and gas from an organic-rich rock formation, in oneembodiment.

FIG. 3 is a cross-sectional view of an illustrative oil shale formationthat is within or connected to groundwater aquifers and a formationleaching operation.

FIG. 4 is a plan view of an illustrative heater well pattern, around aproduction well. Two layers of heater wells are shown.

FIG. 5 is a bar chart comparing one ton of Green River oil shale beforeand after a simulated in situ, retorting process.

FIG. 6 is a process flow diagram of exemplary surface processingfacilities for a subsurface formation development.

FIG. 7 is a graph of the weight percent of each carbon number pseudocomponent occurring from C6 to C38 for laboratory experiments conductedat three different stress levels.

FIG. 8 is a graph of the weight percent ratios of each carbon numberpseudo component occurring from C6 to C38 as compared to the C20 pseudocomponent for laboratory experiments conducted at three different stresslevels.

FIG. 9 is a graph of the weight percent ratios of each carbon numberpseudo component occurring from C6 to C38 as compared to the C25 pseudocomponent for laboratory experiments conducted at three different stresslevels.

FIG. 10 is a graph of the weight percent ratios of each carbon numberpseudo component occurring from C6 to C38 as compared to the C29 pseudocomponent for laboratory experiments conducted at three different stresslevels.

FIG. 11 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from normal-C6 to normal-C38 for laboratoryexperiments conducted at three different stress levels.

FIG. 12 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from normal-C6 to normal-C38 as compared to thenormal-C20 hydrocarbon compound for laboratory experiments conducted atthree different stress levels.

FIG. 13 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from normal-C6 to normal-C38 as compared to thenormal-C25 hydrocarbon compound for laboratory experiments conducted atthree different stress levels.

FIG. 14 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from normal-C6 to normal-C38 as compared to thenormal-C29 hydrocarbon compound for laboratory experiments conducted atthree different stress levels.

FIG. 15 is a graph of the weight ratio of normal alkane hydrocarboncompounds to pseudo components for each carbon number from C6 to C38 forlaboratory experiments conducted at three different stress levels.

FIG. 16 is a bar graph showing the concentration, in molar percentage,of the hydrocarbon species present in the gas samples taken fromduplicate laboratory experiments conducted at three different stresslevels.

FIG. 17 is an exemplary view of the gold tube apparatus used in theunstressed Parr heating test described in Example 1.

FIG. 18 is a cross-sectional view of the Parr vessel used in Examples1-5.

FIG. 19 is gas chromatogram of gas sampled from Example 1.

FIG. 20 is a whole oil gas chromatogram of liquid sampled from Example1.

FIG. 21 is an exemplary view of a Berea cylinder, Berea plugs, and anoil shale core specimen as used in Examples 2-5.

FIG. 22 is an exemplary view of the mini load frame and sample assemblyused in Examples 2-5.

FIG. 23 is gas chromatogram of gas sampled from Example 2.

FIG. 24 is gas chromatogram of gas sampled from Example 3.

FIG. 25 is a whole oil gas chromatogram of liquid sampled from Example3.

FIG. 26 is gas chromatogram of gas sampled from Example 4.

FIG. 27 is a whole oil gas chromatogram of liquid sampled from Example4.

FIG. 28 is gas chromatogram of gas sampled from Example 5.

FIG. 29 is a graph of the weight ratio of each identified compoundoccurring from n-C3 to n-C19 for each of the six 393° C. experiments(Examples 13-19) compared to the weight ratio of each identifiedcompound occurring from n-C3 to n-C19 for Example 13 conducted at 393°C., 500 psig initial argon pressure and 0 psi stress.

FIG. 30 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 393° C. experiments (Examples 13-19) discussed in theExperimental section herein.

FIG. 31 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 375° C. experiments (Examples 6-12) discussed in theExperimental section herein.

FIG. 32 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 375° C. and seven 393° C. experiments (Examples 6-19)discussed in the Experimental section herein.

FIG. 33 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 375° C. and seven 393° C. experiments (Examples 6-19)discussed in the Experimental section herein.

FIG. 34 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number cyclic hydrocarbon compounds for each ofthe seven 393° C. experiments (Examples 13-19) discussed in theExperimental section herein.

FIG. 35 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number cyclic hydrocarbon compounds for each ofthe seven 375° C. and seven 393° C. experiments (Examples 6-19)discussed in the Experimental section herein.

FIG. 36 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number isoprenoid hydrocarbon compounds foreach of the seven 393° C. experiments (Examples 13-19) discussed in theExperimental section herein.

FIG. 37 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number isoprenoid hydrocarbon compounds foreach of the seven 375° C. and seven 393° C. experiments (6-19) discussedin the Experimental section herein.

FIG. 38 is a bar graph of the weight ratio of the certain hydrocarboncompounds to similar carbon number isoprenoid hydrocarbon compounds foreach of the seven 375° C. and seven 393° C. experiments (Examples 6-19)discussed in the Experimental section herein.

FIG. 39 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 6.

FIG. 40 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 7.

FIG. 41 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 8.

FIG. 42 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 9.

FIG. 43 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 10.

FIG. 44 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 11.

FIG. 45 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 12.

FIG. 46 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 13.

FIG. 47 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 14.

FIG. 48 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 15.

FIG. 49 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 16.

FIG. 50 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 17.

FIG. 51 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 18.

FIG. 52 is a C4-C19 GC chromatogram for hydrocarbon liquid sampled inExample 19.

FIG. 53 is a plot of the weight ratio of (trisnorhopane maturable) to(trisnorhopane maturable+trisnorhopane stable) for Examples 6-20.

FIG. 54 is a plot of the weight ratio of [C-29 17α(H), 21β(H) hopane] to[C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] for Examples6-20.

FIG. 55 is a plot of the weight ratio of [C-30 17α(H), 21β(H) hopane] to[C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] for Examples6-20.

FIG. 56 is a plot of the weight ratio of [C-31 17α(H), 21β(H), 22Shomohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H),22R homohopane] for Examples 6-20.

FIG. 57 is a plot of the weight ratio of [C-29 5α, 14α, 17α(H) 20Rsteranes] to [C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20Ssteranes] for examples 6-20.

FIG. 58 is a plot of the weight ratio of [C-29 5α, 14β, 17β(H) 20S+C-295α, 14β, 17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β,17β(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20Rsteranes] for Examples 6-20.

FIG. 59 is a plot of the weight ratio of 3-methyl phenanthrene(3-MP)+2-methyl phenanthrene (2-MP) to 1-methyl phenanthrene(1-MP)+9-methyl phenanthrene (9-MP) for Examples 6-20.

FIG. 60 is a graph of the weight ratio of each identified compoundoccurring from i-C4 to n-C35 for each of the six 393° C. experiments(Examples 13-19) compared to the weight ratio of each identifiedcompound occurring from i-C4 to n-C35 for Example 13 conducted at 393°C., 500 psig initial argon pressure and 0 psi stress.

FIG. 61 is a graph of the weight ratio of each identified compoundoccurring from i-C4 to n-C35 for each of the six 375° C. experiments(Examples 7-12) compared to the weight ratio of each identified compoundoccurring from i-C4 to n-C35 for Example 6 conducted at 375° C., 500psig initial argon pressure and 0 psi stress.

FIG. 62 is a photograph of an unheated oil shale core plug used inexperiments described herein.

FIG. 63 is a photograph of a thin section detail of the unheated oilshale core plug depicted in FIG. 62.

FIG. 64 is a photograph of an oil shale core plug that has been heatedunder no stress as used in experiments described herein.

FIG. 65 is a photograph of a thin section detail of the unstressed andheated oil shale core plug depicted in FIG. 64.

FIG. 66 is a photograph of an oil shale core plug that has been heatedunder stress as used in experiments described herein.

FIG. 67 is a photograph of a thin section detail of the stressed andheated oil shale core plug depicted in FIG. 66.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS Definitions

As used herein, the term “hydrocarbon(s)” refers to organic materialwith molecular structures containing carbon bonded to hydrogen.Hydrocarbons may also include other elements, such as, but not limitedto, halogens, metallic elements, nitrogen, oxygen, and/or sulfur.

As used herein, the term “hydrocarbon fluids” refers to a hydrocarbon ormixtures of hydrocarbons that are gases or liquids. For example,hydrocarbon fluids may include a hydrocarbon or mixtures of hydrocarbonsthat are gases or liquids at formation conditions, at processingconditions or at ambient conditions (15° C. and 1 atm pressure).Hydrocarbon fluids may include, for example, oil, natural gas, coal bedmethane, shale oil, pyrolysis oil, pyrolysis gas, a pyrolysis product ofcoal, and other hydrocarbons that are in a gaseous or liquid state.

As used herein, the terms “produced fluids” and “production fluids”refer to liquids and/or gases removed from a subsurface formation,including, for example, an organic-rich rock formation. Produced fluidsmay include both hydrocarbon fluids and non-hydrocarbon fluids.Production fluids may include, but are not limited to, pyrolyzed shaleoil, synthesis gas, a pyrolysis product of coal, carbon dioxide,hydrogen sulfide and water (including steam). Produced fluids mayinclude both hydrocarbon fluids and non-hydrocarbon fluids.

As used herein, the term “condensable hydrocarbons” means thosehydrocarbons that condense at 25° C. and one atmosphere absolutepressure. Condensable hydrocarbons may include a mixture of hydrocarbonshaving carbon numbers greater than 4.

As used herein, the term “non-condensable hydrocarbons” means thosehydrocarbons that do not condense at 25° C. and one atmosphere absolutepressure. Non-condensable hydrocarbons may include hydrocarbons havingcarbon numbers less than 5.

As used herein, the term “heavy hydrocarbons” refers to hydrocarbonfluids that are highly viscous at ambient conditions (15° C. and 1 atmpressure). Heavy hydrocarbons may include highly viscous hydrocarbonfluids such as heavy oil, tar, and/or asphalt. Heavy hydrocarbons mayinclude carbon and hydrogen, as well as smaller concentrations ofsulfur, oxygen, and nitrogen. Additional elements may also be present inheavy hydrocarbons in trace amounts. Heavy hydrocarbons may beclassified by API gravity. Heavy hydrocarbons generally have an APIgravity below about 20 degrees. Heavy oil, for example, generally has anAPI gravity of about 10-20 degrees, whereas tar generally has an APIgravity below about 10 degrees. The viscosity of heavy hydrocarbons isgenerally greater than about 100 centipoise at 15° C.

As used herein, the term “solid hydrocarbons” refers to any hydrocarbonmaterial that is found naturally in substantially solid form atformation conditions. Non-limiting examples include kerogen, coal,shungites, asphaltites, and natural mineral waxes.

As used herein, the term “formation hydrocarbons” refers to both heavyhydrocarbons and solid hydrocarbons that are contained in anorganic-rich rock formation. Formation hydrocarbons may be, but are notlimited to, kerogen, oil shale, coal, bitumen, tar, natural mineralwaxes, and asphaltites.

As used herein, the term “tar” refers to a viscous hydrocarbon thatgenerally has a viscosity greater than about 10,000 centipoise at 15° C.The specific gravity of tar generally is greater than 1.000. Tar mayhave an API gravity less than 10 degrees.

As used herein, the term “kerogen” refers to a solid, insolublehydrocarbon that principally contains carbon, hydrogen, nitrogen,oxygen, and sulfur. Oil shale contains kerogen.

As used herein, the term “bitumen” refers to a non-crystalline solid orviscous hydrocarbon material that is substantially soluble in carbondisulfide.

As used herein, the term “oil” refers to a hydrocarbon fluid containinga mixture of condensable hydrocarbons.

As used herein, the term “subsurface” refers to geologic strataoccurring below the earth's surface.

As used herein, the term “hydrocarbon-rich formation” refers to anyformation that contains more than trace amounts of hydrocarbons. Forexample, a hydrocarbon-rich formation may include portions that containhydrocarbons at a level of greater than 5 volume percent. Thehydrocarbons located in a hydrocarbon-rich formation may include, forexample, oil, natural gas, heavy hydrocarbons, and solid hydrocarbons.

As used herein, the term “organic-rich rock” refers to any rock matrixholding solid hydrocarbons and/or heavy hydrocarbons. Rock matrices mayinclude, but are not limited to, sedimentary rocks, shales, siltstones,sands, silicilytes, carbonates, and diatomites.

As used herein, the term “formation” refers to any finite subsurfaceregion. The formation may contain one or more hydrocarbon-containinglayers, one or more non-hydrocarbon containing layers, an overburden,and/or an underburden of any subsurface geologic formation. An“overburden” and/or an “underburden” is geological material above orbelow the formation of interest. An overburden or underburden mayinclude one or more different types of substantially impermeablematerials. For example, overburden and/or underburden may include rock,shale, mudstone, or wet/tight carbonate (i.e., an impermeable carbonatewithout hydrocarbons). An overburden and/or an underburden may include ahydrocarbon-containing layer that is relatively impermeable. In somecases, the overburden and/or underburden may be permeable.

As used herein, the term “organic-rich rock formation” refers to anyformation containing organic-rich rock. Organic-rich rock formationsinclude, for example, oil shale formations, coal formations, and tarsands formations.

As used herein, the term “pyrolysis” refers to the breaking of chemicalbonds through the application of heat. For example, pyrolysis mayinclude transforming a compound into one or more other substances byheat alone or by heat in combination with an oxidant. Pyrolysis mayinclude modifying the nature of the compound by addition of hydrogenatoms which may be obtained from molecular hydrogen, water, carbondioxide, or carbon monoxide. Heat may be transferred to a section of theformation to cause pyrolysis.

As used herein, the term “water-soluble minerals” refers to mineralsthat are soluble in water. Water-soluble minerals include, for example,nahcolite (sodium bicarbonate), soda ash (sodium carbonate), dawsonite(NaAl(CO₃)(OH)₂), or combinations thereof. Substantial solubility mayrequire heated water and/or a non-neutral pH solution.

As used herein, the term “formation water-soluble minerals” refers towater-soluble minerals that are found naturally in a formation.

As used herein, the term “migratory contaminant species” refers tospecies that are both soluble or moveable in water or an aqueous fluid,and are considered to be potentially harmful or of concern to humanhealth or the environment. Migratory contaminant species may includeinorganic and organic contaminants. Organic contaminants may includesaturated hydrocarbons, aromatic hydrocarbons, and oxygenatedhydrocarbons. Inorganic contaminants may include metal contaminants, andionic contaminants of various types that may significantly alter pH orthe formation fluid chemistry. Aromatic hydrocarbons may include, forexample, benzene, toluene, xylene, ethylbenzene, and tri-methylbenzene,and various types of polyaromatic hydrocarbons such as anthracenes,naphthalenes, chrysenes and pyrenes. Oxygenated hydrocarbons mayinclude, for example, alcohols, ketones, phenols, and organic acids suchas carboxylic acid. Metal contaminants may include, for example,arsenic, boron, chromium, cobalt, molybdenum, mercury, selenium, lead,vanadium, nickel or zinc. Ionic contaminants include, for example,sulfides, sulfates, chlorides, fluorides, ammonia, nitrates, calcium,iron, magnesium, potassium, lithium, boron, and strontium.

As used herein, the term “cracking” refers to a process involvingdecomposition and molecular recombination of organic compounds toproduce a greater number of molecules than were initially present. Incracking, a series of reactions take place accompanied by a transfer ofhydrogen atoms between molecules. For example, naphtha may undergo athermal cracking reaction to form ethene and H₂ among other molecules.

As used herein, the term “sequestration” refers to the storing of afluid that is a by-product of a process rather than discharging thefluid to the atmosphere or open environment.

As used herein, the term “subsidence” refers to a downward movement of asurface relative to an initial elevation of the surface.

As used herein, the term “thickness” of a layer refers to the distancebetween the upper and lower boundaries of a cross section of a layer,wherein the distance is measured normal to the average tilt of the crosssection.

As used herein, the term “thermal fracture” refers to fractures createdin a formation caused directly or indirectly by expansion or contractionof a portion of the formation and/or fluids within the formation, whichin turn is caused by increasing/decreasing the temperature of theformation and/or fluids within the formation, and/or byincreasing/decreasing a pressure of fluids within the formation due toheating. Thermal fractures may propagate into or form in neighboringregions significantly cooler than the heated zone.

As used herein, the term “hydraulic fracture” refers to a fracture atleast partially propagated into a formation, wherein the fracture iscreated through injection of pressurized fluids into the formation. Thefracture may be artificially held open by injection of a proppantmaterial. Hydraulic fractures may be substantially horizontal inorientation, substantially vertical in orientation, or oriented alongany other plane.

As used herein, the term “wellbore” refers to a hole in the subsurfacemade by drilling or insertion of a conduit into the subsurface. Awellbore may have a substantially circular cross section, or othercross-sectional shapes (e.g., circles, ovals, squares, rectangles,triangles, slits, or other regular or irregular shapes). As used herein,the term “well”, when referring to an opening in the formation, may beused interchangeably with the term “wellbore.”

DESCRIPTION OF SPECIFIC EMBODIMENTS

The inventions are described herein in connection with certain specificembodiments. However, to the extent that the following detaileddescription is specific to a particular embodiment or a particular use,such is intended to be illustrative only and is not to be construed aslimiting the scope of the invention.

As discussed herein, some embodiments of the invention include or haveapplication related to an in situ method of recovering naturalresources. The natural resources may be recovered from an organic-richrock formation, including, for example, an oil shale formation. Theorganic-rich rock formation may include formation hydrocarbons,including, for example, kerogen, coal, and heavy hydrocarbons. In someembodiments of the invention the natural resources may includehydrocarbon fluids, including, for example, products of the pyrolysis offormation hydrocarbons such as shale oil. In some embodiments of theinvention the natural resources may also include water-soluble minerals,including, for example, nahcolite (sodium bicarbonate, or 2NaHCO₃), sodaash (sodium carbonate, or Na₂CO₃) and dawsonite (NaAl(CO₃)(OH)₂).

FIG. 1 presents a perspective view of an illustrative oil shaledevelopment area 10. A surface 12 of the development area 10 isindicated. Below the surface is an organic-rich rock formation 16. Theillustrative subsurface formation 16 contains formation hydrocarbons(such as, for example, kerogen) and possibly valuable water-solubleminerals (such as, for example, nahcolite). It is understood that therepresentative formation 16 may be any organic-rich rock formation,including a rock matrix containing coal or tar sands, for example. Inaddition, the rock matrix making up the formation 16 may be permeable,semi-permeable or non-permeable. The present inventions are particularlyadvantageous in oil shale development areas initially having verylimited or effectively no fluid permeability.

In order to access formation 16 and recover natural resources therefrom,a plurality of wellbores is formed. Wellbores are shown at 14 in FIG. 1.The representative wellbores 14 are essentially vertical in orientationrelative to the surface 12. However, it is understood that some or allof the wellbores 14 could deviate into an obtuse or even horizontalorientation. In the arrangement of FIG. 1, each of the wellbores 14 iscompleted in the oil shale formation 16. The completions may be eitheropen or cased hole. The well completions may also include propped orunpropped hydraulic fractures emanating therefrom.

In the view of FIG. 1, only seven wellbores 14 are shown. However, it isunderstood that in an oil shale development project, numerous additionalwellbores 14 will most likely be drilled. The wellbores 14 may belocated in relatively close proximity, being from 10 feet to up to 300feet in separation. In some embodiments, a well spacing of 15 to 25 feetis provided. Typically, the wellbores 14 are also completed at shallowdepths, being from 200 to 5,000 feet at total depth. In some embodimentsthe oil shale formation targeted for in situ retorting is at a depthgreater than 200 feet below the surface or alternatively 400 feet belowthe surface. Alternatively, conversion and production occur at depthsbetween 500 and 2,500 feet.

The wellbores 14 will be selected for certain functions and may bedesignated as heat injection wells, water injection wells, oilproduction wells and/or water-soluble mineral solution production wells.In one aspect, the wellbores 14 are dimensioned to serve two, three, orall four of these purposes. Suitable tools and equipment may besequentially run into and removed from the wellbores 14 to serve thevarious purposes.

A fluid processing facility 17 is also shown schematically. The fluidprocessing facility 17 is equipped to receive fluids produced from theorganic-rich rock formation 16 through one or more pipelines or flowlines 18. The fluid processing facility 17 may include equipmentsuitable for receiving and separating oil, gas, and water produced fromthe heated formation. The fluid processing facility 17 may furtherinclude equipment for separating out dissolved water-soluble mineralsand/or migratory contaminant species, including, for example, dissolvedorganic contaminants, metal contaminants, or ionic contaminants in theproduced water recovered from the organic-rich rock formation 16. Thecontaminants may include, for example, aromatic hydrocarbons such asbenzene, toluene, xylene, and tri-methylbenzene. The contaminants mayalso include polyaromatic hydrocarbons such as anthracene, naphthalene,chrysene and pyrene. Metal contaminants may include species containingarsenic, boron, chromium, mercury, selenium, lead, vanadium, nickel,cobalt, molybdenum, or zinc. Ionic contaminant species may include, forexample, sulfates, chlorides, fluorides, lithium, potassium, aluminum,ammonia, and nitrates.

In order to recover oil, gas, and sodium (or other) water-solubleminerals, a series of steps may be undertaken. FIG. 2 presents a flowchart demonstrating a method of in situ thermal recovery of oil and gasfrom an organic-rich rock formation 100, in one embodiment. It isunderstood that the order of some of the steps from FIG. 2 may bechanged, and that the sequence of steps is merely for illustration.

First, the oil shale (or other organic-rich rock) formation 16 isidentified within the development area 10. This step is shown in box110. Optionally, the oil shale formation may contain nahcolite or othersodium minerals. The targeted development area within the oil shaleformation may be identified by measuring or modeling the depth,thickness and organic richness of the oil shale as well as evaluatingthe position of the organic-rich rock formation relative to other rocktypes, structural features (e.g. faults, anticlines or synclines), orhydrogeological units (i.e. aquifers). This is accomplished by creatingand interpreting maps and/or models of depth, thickness, organicrichness and other data from available tests and sources. This mayinvolve performing geological surface surveys, studying outcrops,performing seismic surveys, and/or drilling boreholes to obtain coresamples from subsurface rock. Rock samples may be analyzed to assesskerogen content and hydrocarbon fluid generating capability.

The kerogen content of the organic-rich rock formation may beascertained from outcrop or core samples using a variety of data. Suchdata may include organic carbon content, hydrogen index, and modifiedFischer assay analyses. Subsurface permeability may also be assessed viarock samples, outcrops, or studies of ground water flow. Furthermore theconnectivity of the development area to ground water sources may beassessed.

Next, a plurality of wellbores 14 is formed across the targeteddevelopment area 10. This step is shown schematically in box 115. Thepurposes of the wellbores 14 are set forth above and need not berepeated. However, it is noted that for purposes of the wellboreformation step of box 115, only a portion of the wells need be completedinitially. For instance, at the beginning of the project heat injectionwells are needed, while a majority of the hydrocarbon production wellsare not yet needed. Production wells may be brought in once conversionbegins, such as after 4 to 12 months of heating.

It is understood that petroleum engineers will develop a strategy forthe best depth and arrangement for the wellbores 14, depending uponanticipated reservoir characteristics, economic constraints, and workscheduling constraints. In addition, engineering staff will determinewhat wellbores 14 shall be used for initial formation 16 heating. Thisselection step is represented by box 120.

Concerning heat injection wells, there are various methods for applyingheat to the organic-rich rock formation 16. The present methods are notlimited to the heating technique employed unless specifically so statedin the claims. The heating step is represented generally by box 130.Preferably, for in situ processes the heating of a production zone takesplace over a period of months, or even four or more years.

The formation 16 is heated to a temperature sufficient to pyrolyze atleast a portion of the oil shale in order to convert the kerogen tohydrocarbon fluids. The bulk of the target zone of the formation may beheated to between 270° C. to 800° C. Alternatively, the targeted volumeof the organic-rich formation is heated to at least 350° C. to createproduction fluids. The conversion step is represented in FIG. 2 by box135. The resulting liquids and hydrocarbon gases may be refined intoproducts which resemble common commercial petroleum products. Suchliquid products include transportation fuels such as diesel, jet fueland naptha. Generated gases include light alkanes, light alkenes, H₂,CO₂, CO, and NH₃.

Conversion of the oil shale will create permeability in the oil shalesection in rocks that were originally impermeable. Preferably, theheating and conversion processes of boxes 130 and 135, occur over alengthy period of time. In one aspect, the heating period is from threemonths to four or more years. Also as an optional part of box 135, theformation 16 may be heated to a temperature sufficient to convert atleast a portion of nahcolite, if present, to soda ash. Heat applied tomature the oil shale and recover oil and gas will also convert nahcoliteto sodium carbonate (soda ash), a related sodium mineral. The process ofconverting nahcolite (sodium bicarbonate) to soda ash (sodium carbonate)is described herein.

In connection with the heating step 130, the rock formation 16 mayoptionally be fractured to aid heat transfer or later hydrocarbon fluidproduction. The optional fracturing step is shown in box 125. Fracturingmay be accomplished by creating thermal fractures within the formationthrough application of heat. By heating the organic-rich rock andtransforming the kerogen to oil and gas, the permeability of portions ofthe formation are increased via thermal fracture formation andsubsequent production of a portion of the hydrocarbon fluids generatedfrom the kerogen. Alternatively, a process known as hydraulic fracturingmay be used. Hydraulic fracturing is a process known in the art of oiland gas recovery where a fracture fluid is pressurized within thewellbore above the fracture pressure of the formation, thus developingfracture planes within the formation to relieve the pressure generatedwithin the wellbore. Hydraulic fractures may be used to createadditional permeability in portions of the formation and/or be used toprovide a planar source for heating.

As part of the hydrocarbon fluid production process 100, certain wells14 may be designated as oil and gas production wells. This step isdepicted by box 140. Oil and gas production might not be initiated untilit is determined that the kerogen has been sufficiently retorted toallow maximum recovery of oil and gas from the formation 16. In someinstances, dedicated production wells are not drilled until after heatinjection wells (box 130) have been in operation for a period of severalweeks or months. Thus, box 140 may include the formation of additionalwellbores 14. In other instances, selected heater wells are converted toproduction wells.

After certain wellbores 14 have been designated as oil and gasproduction wells, oil and/or gas is produced from the wellbores 14. Theoil and/or gas production process is shown at box 145. At this stage(box 145), any water-soluble minerals, such as nahcolite and convertedsoda ash may remain substantially trapped in the rock formation 16 asfinely disseminated crystals or nodules within the oil shale beds, andare not produced. However, some nahcolite and/or soda ash may bedissolved in the water created during heat conversion (box 135) withinthe formation.

Box 150 presents an optional next step in the oil and gas recoverymethod 100. Here, certain wellbores 14 are designated as water oraqueous fluid injection wells. Aqueous fluids are solutions of waterwith other species. The water may constitute “brine,” and may includedissolved inorganic salts of chloride, sulfates and carbonates of GroupI and II elements of The Periodic Table of Elements. Organic salts canalso be present in the aqueous fluid. The water may alternatively befresh water containing other species. The other species may be presentto alter the pH. Alternatively, the other species may reflect theavailability of brackish water not saturated in the species wished to beleached from the subsurface. Preferably, the water injection wells areselected from some or all of the wellbores used for heat injection orfor oil and/or gas production. However, the scope of the step of box 150may include the drilling of yet additional wellbores 14 for use asdedicated water injection wells. In this respect, it may be desirable tocomplete water injection wells along a periphery of the development area10 in order to create a boundary of high pressure.

Next, optionally water or an aqueous fluid is injected through the waterinjection wells and into the oil shale formation 16. This step is shownat box 155. The water may be in the form of steam or pressurized hotwater. Alternatively the injected water may be cool and becomes heatedas it contacts the previously heated formation. The injection processmay further induce fracturing. This process may create fingered cavernsand brecciated zones in the nahcolite-bearing intervals some distance,for example up to 200 feet out, from the water injection wellbores. Inone aspect, a gas cap, such as nitrogen, may be maintained at the top ofeach “cavern” to prevent vertical growth.

Along with the designation of certain wellbores 14 as water injectionwells, the design engineers may also designate certain wellbores 14 aswater or water-soluble mineral solution production wells. This step isshown in box 160. These wells may be the same as wells used topreviously produce hydrocarbons or inject heat. These recovery wells maybe used to produce an aqueous solution of dissolved water-solubleminerals and other species, including, for example, migratorycontaminant species. For example, the solution may be one primarily ofdissolved soda ash. This step is shown in box 165. Alternatively, singlewellbores may be used to both inject water and then to recover a sodiummineral solution. Thus, box 165 includes the option of using the samewellbores 14 for both water injection and solution production (Box 165).

Temporary control of the migration of the migratory contaminant species,especially during the pyrolysis process, can be obtained via placementof the injection and production wells 14 such that fluid flow out of theheated zone is minimized. Typically, this involves placing injectionwells at the periphery of the heated zone so as to cause pressuregradients which prevent flow inside the heated zone from leaving thezone.

FIG. 3 is a cross-sectional view of an illustrative oil shale formationthat is within or connected to ground water aquifers and a formationleaching operation. Four separate oil shale formation zones are depicted(23, 24, 25 and 26) within the oil shale formation. The water aquifersare below the ground surface 27, and are categorized as an upper aquifer20 and a lower aquifer 22. Intermediate the upper and lower aquifers isan aquitard 21. It can be seen that certain zones of the formation areboth aquifers or aquitards and oil shale zones. A plurality of wells(28, 29, 30 and 31) is shown traversing vertically downward through theaquifers. One of the wells is serving as a water injection well 31,while another is serving as a water production well 30. In this way,water is circulated 32 through at least the lower aquifer 22.

FIG. 3 shows diagrammatically the water circulation 32 through an oilshale volume that was heated 33, that resides within or is connected toan aquifer 22, and from which hydrocarbon fluids were previouslyrecovered. Introduction of water via the water injection well 31 forceswater into the previously heated oil shale 33 and water-soluble mineralsand migratory contaminants species are swept to the water productionwell 30. The water may then be processed in a facility 34 wherein thewater-soluble minerals (e.g. nahcolite or soda ash) and the migratorycontaminants may be substantially removed from the water stream. Wateris then reinjected into the oil shale volume 33 and the formationleaching is repeated. This leaching with water is intended to continueuntil levels of migratory contaminant species are at environmentallyacceptable levels within the previously heated oil shale zone 33. Thismay require 1 cycle, 2 cycles, 5 cycles 10 cycles or more cycles offormation leaching, where a single cycle indicates injection andproduction of approximately one pore volume of water. It is understoodthat there may be numerous water injection and water production wells inan actual oil shale development. Moreover, the system may includemonitoring wells (28 and 29) which can be utilized during the oil shaleheating phase, the shale oil production phase, the leaching phase, orduring any combination of these phases to monitor for migratorycontaminant species and/or water-soluble minerals.

In order to expand upon various features and methods for shale oildevelopment, certain sections are specifically entitled below.

In some fields, formation hydrocarbons, such as oil shale, may exist inmore than one subsurface formation. In some instances, the organic-richrock formations may be separated by rock layers that arehydrocarbon-free or that otherwise have little or no commercial value.Therefore, it may be desirable for the operator of a field underhydrocarbon development to undertake an analysis as to which of thesubsurface, organic-rich rock formations to target or in which orderthey should be developed.

The organic-rich rock formation may be selected for development based onvarious factors. One such factor is the thickness of the hydrocarboncontaining layer within the formation. Greater pay zone thickness mayindicate a greater potential volumetric production of hydrocarbonfluids. Each of the hydrocarbon containing layers may have a thicknessthat varies depending on, for example, conditions under which theformation hydrocarbon containing layer was formed. Therefore, anorganic-rich rock formation will typically be selected for treatment ifthat formation includes at least one formation hydrocarbon-containinglayer having a thickness sufficient for economical production ofproduced fluids.

An organic-rich rock formation may also be chosen if the thickness ofseveral layers that are closely spaced together is sufficient foreconomical production of produced fluids. For example, an in situconversion process for formation hydrocarbons may include selecting andtreating a layer within an organic-rich rock formation having athickness of greater than about 5 meters, 10 meters, 50 m, or even 100meters. In this manner, heat losses (as a fraction of total injectedheat) to layers formed above and below an organic-rich rock formationmay be less than such heat losses from a thin layer of formationhydrocarbons. A process as described herein, however, may also includeselecting and treating layers that may include layers substantially freeof formation hydrocarbons or thin layers of formation hydrocarbons.

The richness of one or more organic-rich rock formations may also beconsidered. Richness may depend on many factors including the conditionsunder which the formation hydrocarbon containing layer was formed, anamount of formation hydrocarbons in the layer, and/or a composition offormation hydrocarbons in the layer. A thin and rich formationhydrocarbon layer may be able to produce significantly more valuablehydrocarbons than a much thicker, less rich formation hydrocarbon layer.Of course, producing hydrocarbons from a formation that is both thickand rich is desirable.

The kerogen content of an organic-rich rock formation may be ascertainedfrom outcrop or core samples using a variety of data. Such data mayinclude organic carbon content, hydrogen index, and modified Fischerassay analyses. The Fischer Assay is a standard method which involvesheating a sample of a formation hydrocarbon containing layer toapproximately 500° C. in one hour, collecting fluids produced from theheated sample, and quantifying the amount of fluids produced.

Subsurface formation permeability may also be assessed via rock samples,outcrops, or studies of ground water flow. Furthermore the connectivityof the development area to ground water sources may be assessed. Thus,an organic-rich rock formation may be chosen for development based onthe permeability or porosity of the formation matrix even if thethickness of the formation is relatively thin.

Other factors known to petroleum engineers may be taken intoconsideration when selecting a formation for development. Such factorsinclude depth of the perceived pay zone, stratigraphic proximity offresh ground water to kerogen-containing zones, continuity of thickness,and other factors. For instance, the assessed fluid production contentwithin a formation will also effect eventual volumetric production.

In producing hydrocarbon fluids from an oil shale field, it may bedesirable to control the migration of pyrolyzed fluids. In someinstances, this includes the use of injection wells, particularly aroundthe periphery of the field. Such wells may inject water, steam, CO₂,heated methane, or other fluids to drive cracked kerogen fluids inwardlytowards production wells. In some embodiments, physical barriers may beplaced around the area of the organic-rich rock formation underdevelopment. One example of a physical barrier involves the creation offreeze walls. Freeze walls are formed by circulating refrigerant throughperipheral wells to substantially reduce the temperature of the rockformation. This, in turn, prevents the pyrolyzation of kerogen presentat the periphery of the field and the outward migration of oil and gas.Freeze walls will also cause native water in the formation along theperiphery to freeze.

The use of subsurface freezing to stabilize poorly consolidated soils orto provide a barrier to fluid flow is known in the art. ShellExploration and Production Company has discussed the use of freeze wallsfor oil shale production in several patents, including U.S. Pat. No.6,880,633 and U.S. Pat. No. 7,032,660. Shell's '660 patent usessubsurface freezing to protect against groundwater flow and groundwatercontamination during in situ shale oil production. Additional patentsthat disclose the use of so-called freeze walls are U.S. Pat. No.3,528,252, U.S. Pat. No. 3,943,722, U.S. Pat. No. 3,729,965, U.S. Pat.No. 4,358,222, U.S. Pat. No. 4,607,488.

Another example of a physical barrier that may be used to limit fluidflow into or out of an oil shale field is the creation of grout walls.Grout walls are formed by injecting cement into the formation to fillpermeable pathways. In the context of an oil shale field, cement wouldbe injected along the periphery of the field. This prevents the movementof pyrolyzed fluids out of the field under development, and the movementof water from adjacent aquifers into the field.

As noted above, several different types of wells may be used in thedevelopment of an organic-rich rock formation, including, for example,an oil shale field. For example, the heating of the organic-rich rockformation may be accomplished through the use of heater wells. Theheater wells may include, for example, electrical resistance heatingelements. The production of hydrocarbon fluids from the formation may beaccomplished through the use of wells completed for the production offluids. The injection of an aqueous fluid may be accomplished throughthe use of injection wells. Finally, the production of an aqueoussolution may be accomplished through use of solution production wells.

The different wells listed above may be used for more than one purpose.Stated another way, wells initially completed for one purpose may laterbe used for another purpose, thereby lowering project costs and/ordecreasing the time required to perform certain tasks. For example, oneor more of the production wells may also be used as injection wells forlater injecting water into the organic-rich rock formation.Alternatively, one or more of the production wells may also be used assolution production wells for later producing an aqueous solution fromthe organic-rich rock formation.

In other aspects, production wells (and in some circumstances heaterwells) may initially be used as dewatering wells (e.g., before heatingis begun and/or when heating is initially started). In addition, in somecircumstances dewatering wells can later be used as production wells(and in some circumstances heater wells). As such, the dewatering wellsmay be placed and/or designed so that such wells can be later used asproduction wells and/or heater wells. The heater wells may be placedand/or designed so that such wells can be later used as production wellsand/or dewatering wells. The production wells may be placed and/ordesigned so that such wells can be later used as dewatering wells and/orheater wells. Similarly, injection wells may be wells that initiallywere used for other purposes (e.g., heating, production, dewatering,monitoring, etc.), and injection wells may later be used for otherpurposes. Similarly, monitoring wells may be wells that initially wereused for other purposes (e.g., heating, production, dewatering,injection, etc.). Finally, monitoring wells may later be used for otherpurposes such as water production.

The wellbores for the various wells may be located in relatively closeproximity, being from 10 feet to up to 300 feet in separation.Alternatively, the wellbores may be spaced from 30 to 200 feet or 50 to100 feet. Typically, the wellbores are also completed at shallow depths,being from 200 to 5,000 feet at total depth. Alternatively, thewellbores may be completed at depths from 1,000 to 4,000 feet, or 1,500to 3,500 feet. In some embodiments, the oil shale formation targeted forin situ retorting is at a depth greater than 200 feet below the surface.In alternative embodiments, the oil shale formation targeted for in situretorting is at a depth greater than 500, 1,000, or 1,500 feet below thesurface. In alternative embodiments, the oil shale formation targetedfor in situ retorting is at a depth between 200 and 5,000 feet,alternatively between 1,000 and 4,000 ft, 1,200 and 3,700 feet, or 1,500and 3,500 feet below the surface.

It is desirable to arrange the various wells for an oil shale field in apre-planned pattern. For instance, heater wells may be arranged in avariety of patterns including, but not limited to triangles, squares,hexagons, and other polygons. The pattern may include a regular polygonto promote uniform heating through at least the portion of the formationin which the heater wells are placed. The pattern may also be a linedrive pattern. A line drive pattern generally includes a first lineararray of heater wells, a second linear array of heater wells, and aproduction well or a linear array of production wells between the firstand second linear array of heater wells. Interspersed among the heaterwells are typically one or more production wells. The injection wellsmay likewise be disposed within a repetitive pattern of units, which maybe similar to or different from that used for the heater wells.

One method to reduce the number of wells is to use a single well as botha heater well and a production well. Reduction of the number of wells byusing single wells for sequential purposes can reduce project costs. Oneor more monitoring wells may be disposed at selected points in thefield. The monitoring wells may be configured with one or more devicesthat measure a temperature, a pressure, and/or a property of a fluid inthe wellbore. In some instances, a heater well may also serve as amonitoring well, or otherwise be instrumented.

Another method for reducing the number of heater wells is to use wellpatterns. Regular patterns of heater wells equidistantly spaced from aproduction well may be used. The patterns may form equilateraltriangular arrays, hexagonal arrays, or other array patterns. The arraysof heater wells may be disposed such that a distance between each heaterwell is less than about 70 feet (21 m). A portion of the formation maybe heated with heater wells disposed substantially parallel to aboundary of the hydrocarbon formation.

In alternative embodiments, the array of heater wells may be disposedsuch that a distance between each heater well may be less than about 100feet, or 50 feet, or 30 feet. Regardless of the arrangement of ordistance between the heater wells, in certain embodiments, a ratio ofheater wells to production wells disposed within a organic-rich rockformation may be greater than about 5, 8, 10, 20, or more.

In one embodiment, individual production wells are surrounded by at mostone layer of heater wells. This may include arrangements such as 5-spot,7-spot, or 9-spot arrays, with alternating rows of production and heaterwells. In another embodiment, two layers of heater wells may surround aproduction well, but with the heater wells staggered so that a clearpathway exists for the majority of flow away from the further heaterwells. Flow and reservoir simulations may be employed to assess thepathways and temperature history of hydrocarbon fluids generated in situas they migrate from their points of origin to production wells.

FIG. 4 provides a plan view of an illustrative heater well arrangementusing more than one layer of heater wells. The heater well arrangementis used in connection with the production of hydrocarbons from a shaleoil development area 400. In FIG. 4, the heater well arrangement employsa first layer of heater wells 410, surrounded by a second layer ofheater wells 420. The heater wells in the first layer 410 are referencedat 431, while the heater wells in the second layer 420 are referenced at432.

A production well 440 is shown central to the well layers 410 and 420.It is noted that the heater wells 432 in the second layer 420 of wellsare offset from the heater wells 431 in the first layer 410 of wells,relative to the production well 440. The purpose is to provide aflowpath for converted hydrocarbons that minimizes travel near a heaterwell in the first layer 410 of heater wells. This, in turn, minimizessecondary cracking of hydrocarbons converted from kerogen ashydrocarbons flow from the second layer of wells 420 to the productionwells 440.

In the illustrative arrangement of FIG. 4, the first layer 410 and thesecond layer 420 each defines a 5-spot pattern. However, it isunderstood that other patterns may be employed, such as 3-spot or 6-spotpatterns. In any instance, a plurality of heater wells 431 comprising afirst layer of heater wells 410 is placed around a production well 440,with a second plurality of heater wells 432 comprising a second layer ofheater wells 420 placed around the first layer 410.

The heater wells in the two layers also may be arranged such that themajority of hydrocarbons generated by heat from each heater well 432 inthe second layer 420 are able to migrate to a production well 440without passing substantially near a heater well 431 in the first layer410. The heater wells 431, 432 in the two layers 410, 420 further may bearranged such that the majority of hydrocarbons generated by heat fromeach heater well 432 in the second layer 420 are able to migrate to theproduction well 440 without passing through a zone of substantiallyincreasing formation temperature.

One method to reduce the number of heater wells is to use well patternsthat are elongated in a particular direction, particularly in thedirection of most efficient thermal conductivity. Heat convection may beaffected by various factors such as bedding planes and stresses withinthe formation. For instance, heat convection may be more efficient inthe direction perpendicular to the least horizontal principal stress onthe formation. In some instanced, heat convection may be more efficientin the direction parallel to the least horizontal principal stress.

In connection with the development of an oil shale field, it may bedesirable that the progression of heat through the subsurface inaccordance with steps 130 and 135 be uniform. However, for variousreasons the heating and maturation of formation hydrocarbons in asubsurface formation may not proceed uniformly despite a regulararrangement of heater and production wells. Heterogeneities in the oilshale properties and formation structure may cause certain local areasto be more or less productive. Moreover, formation fracturing whichoccurs due to the heating and maturation of the oil shale can lead to anuneven distribution of preferred pathways and, thus, increase flow tocertain production wells and reduce flow to others. Uneven fluidmaturation may be an undesirable condition since certain subsurfaceregions may receive more heat energy than necessary where other regionsreceive less than desired. This, in turn, leads to the uneven flow andrecovery of production fluids. Produced oil quality, overall productionrate, and/or ultimate recoveries may be reduced.

To detect uneven flow conditions, production and heater wells may beinstrumented with sensors. Sensors may include equipment to measuretemperature, pressure, flow rates, and/or compositional information.Data from these sensors can be processed via simple rules or input todetailed simulations to reach decisions on how to adjust heater andproduction wells to improve subsurface performance. Production wellperformance may be adjusted by controlling backpressure or throttling onthe well. Heater well performance may also be adjusted by controllingenergy input. Sensor readings may also sometimes imply mechanicalproblems with a well or downhole equipment which requires repair,replacement, or abandonment.

In one embodiment, flow rate, compositional, temperature and/or pressuredata are utilized from two or more wells as inputs to a computeralgorithm to control heating rate and/or production rates. Unmeasuredconditions at or in the neighborhood of the well are then estimated andused to control the well. For example, in situ fracturing behavior andkerogen maturation are estimated based on thermal, flow, andcompositional data from a set of wells. In another example, wellintegrity is evaluated based on pressure data, well temperature data,and estimated in situ stresses. In a related embodiment the number ofsensors is reduced by equipping only a subset of the wells withinstruments, and using the results to interpolate, calculate, orestimate conditions at uninstrumented wells. Certain wells may have onlya limited set of sensors (e.g., wellhead temperature and pressure only)where others have a much larger set of sensors (e.g., wellheadtemperature and pressure, bottomhole temperature and pressure,production composition, flow rate, electrical signature, casing strain,etc.).

As noted above, there are various methods for applying heat to anorganic-rich rock formation. For example, one method may includeelectrical resistance heaters disposed in a wellbore or outside of awellbore. One such method involves the use of electrical resistiveheating elements in a cased or uncased wellbore. Electrical resistanceheating involves directly passing electricity through a conductivematerial such that resistive losses cause it to heat the conductivematerial. Other heating methods include the use of downhole combustors,in situ combustion, radio-frequency (RF) electrical energy, or microwaveenergy. Still others include injecting a hot fluid into the oil shaleformation to directly heat it. The hot fluid may or may not becirculated. One method may include generating heat by burning a fuelexternal to or within a subsurface formation. For example, heat may besupplied by surface burners or downhole burners or by circulating hotfluids (such as methane gas or naphtha) into the formation through, forexample, wellbores via, for example, natural or artificial fractures.Some burners may be configured to perform flameless combustion.Alternatively, some methods may include combusting fuel within theformation such as via a natural distributed combustor, which generallyrefers to a heater that uses an oxidant to oxidize at least a portion ofthe carbon in the formation to generate heat, and wherein the oxidationtakes place in a vicinity proximate to a wellbore. The present methodsare not limited to the heating technique employed unless so stated inthe claims.

One method for formation heating involves the use of electricalresistors in which an electrical current is passed through a resistivematerial which dissipates the electrical energy as heat. This method isdistinguished from dielectric heating in which a high-frequencyoscillating electric current induces electrical currents in nearbymaterials and causes them to heat. The electric heater may include aninsulated conductor, an elongated member disposed in the opening, and/ora conductor disposed in a conduit. An early patent disclosing the use ofelectrical resistance heaters to produce oil shale in situ is U.S. Pat.No. 1,666,488. The '488 patent issued to Crawshaw in 1928. Since 1928,various designs for downhole electrical heaters have been proposed.Illustrative designs are presented in U.S. Pat. No. 1,701,884, U.S. Pat.No. 3,376,403, U.S. Pat. No. 4,626,665, U.S. Pat. No. 4,704,514, andU.S. Pat. No. 6,023,554).

A review of application of electrical heating methods for heavy oilreservoirs is given by R. Sierra and S. M. Farouq Ali, “PromisingProgress in Field Application of Reservoir Electrical Heating Methods”,Society of Petroleum Engineers Paper 69709, 2001. The entire disclosureof this reference is hereby incorporated by reference.

Certain previous designs for in situ electrical resistance heatersutilized solid, continuous heating elements (e.g., metal wires orstrips). However, such elements may lack the necessary robustness forlong-term, high temperature applications such as oil shale maturation.As the formation heats and the oil shale matures, significant expansionof the rock occurs. This leads to high stresses on wells intersectingthe formation. These stresses can lead to bending and stretching of thewellbore pipe and internal components. Cementing (e.g., U.S. Pat. No.4,886,118) or packing (e.g., U.S. Pat. No. 2,732,195) a heating elementin place may provide some protection against stresses, but some stressesmay still be transmitted to the heating element.

As an alternative, U.S. Pat. No. 7,331,385 teaches the use ofelectrically conductive fractures to heat the oil shale. A heatingelement is constructed by forming wellbores and then hydraulicallyfracturing the oil shale formation around the wellbores. The fracturesare filled with an electrically conductive material which forms theheating element. Calcined petroleum coke is an exemplary suitableconductant material. Preferably, the fractures are created in a verticalorientation along longitudinal, horizontal planes formed by horizontalwellbores. Electricity may be conducted through the conductive fracturesfrom the heel to the toe of each well. The electrical circuit may becompleted by an additional horizontal well that intersects one or moreof the vertical fractures near the toe to supply the opposite electricalpolarity. The U.S. Pat. No. 7,331,385 process creates an “in situtoaster” that artificially matures oil shale through the application ofelectric heat. Thermal conduction heats the oil shale to conversiontemperatures in excess of 300° C. causing artificial maturation.

U.S. Pat. No. 7,441,603 teaches an alternative heating means thatemploys the circulation of a heated fluid within an oil shale formation.In the process of U.S. Pat. No. 7,441,603 supercritical heated naphthamay be circulated through fractures in the formation. This means thatthe oil shale is heated by circulating a dense, hot hydrocarbon vaporthrough sets of closely-spaced hydraulic fractures. In one aspect, thefractures are horizontally formed and conventionally propped. Fracturetemperatures of 320°-400° C. are maintained for up to five to ten years.Vaporized naptha may be the preferred heating medium due to its highvolumetric heat capacity, ready availability and relatively lowdegradation rate at the heating temperature. In the U.S. Pat. No.7,441,603 process, as the kerogen matures, fluid pressure will drive thegenerated oil to the heated fractures, where it will be produced withthe cycling hydrocarbon vapor.

The purpose for heating the organic-rich rock formation is to pyrolyzeat least a portion of the solid formation hydrocarbons to createhydrocarbon fluids. The solid formation hydrocarbons may be pyrolyzed insitu by raising the organic-rich rock formation, (or zones within theformation), to a pyrolyzation temperature. In certain embodiments, thetemperature of the formation may be slowly raised through the pyrolysistemperature range. For example, an in situ conversion process mayinclude heating at least a portion of the organic-rich rock formation toraise the average temperature of the zone above about 270° C. at a rateless than a selected amount (e.g., about 10° C., 5° C.; 3° C., 1° C.,0.5° C., or 0.1° C.) per day. In a further embodiment, the portion maybe heated such that an average temperature of the selected zone may beless than about 375° C. or, in some embodiments, less than about 400° C.The formation may be heated such that a temperature within the formationreaches (at least) an initial pyrolyzation temperature (e.g., atemperature at the lower end of the temperature range where pyrolyzationbegins to occur.

The pyrolysis temperature range may vary depending on the types offormation hydrocarbons within the formation, the heating methodology,and the distribution of heating sources. For example, a pyrolysistemperature range may include temperatures between about 270° C. andabout 900° C. Alternatively, the bulk of the target zone of theformation may be heated to between 300° to 600° C. In an alternativeembodiment, a pyrolysis temperature range may include temperaturesbetween about 270° C. to about 500° C.

Preferably, for in situ processes the heating of a production zone takesplace over a period of months, or even four or more years.Alternatively, the formation may be heated for one to fifteen years,alternatively, 3 to 10 years, 1.5 to 7 years, or 2 to 5 years. The bulkof the target zone of the formation may be heated to between 270° to800° C. Preferably, the bulk of the target zone of the formation isheated to between 300° to 600° C. Alternatively, the bulk of the targetzone is ultimately heated to a temperature below 400° C. (752° F.).

In certain embodiments of the methods of the present invention, downholeburners may be used to heat a targeted oil shale zone. Downhole burnersof various design have been discussed in the patent literature for usein oil shale and other largely solid hydrocarbon deposits. Examplesinclude U.S. Pat. No. 2,887,160; U.S. Pat. No. 2,847,071; U.S. Pat. No.2,895,555; U.S. Pat. No. 3,109,482; U.S. Pat. No. 3,225,829; U.S. Pat.No. 3,241,615; U.S. Pat. No. 3,254,721; U.S. Pat. No. 3,127,936; U.S.Pat. No. 3,095,031; U.S. Pat. No. 5,255,742; and U.S. Pat. No.5,899,269. Downhole burners operate through the transport of acombustible fuel (typically natural gas) and an oxidizer (typically air)to a subsurface position in a wellbore. The fuel and oxidizer reactdownhole to generate heat. The combustion gases are removed (typicallyby transport to the surface, but possibly via injection into theformation). Oftentimes, downhole burners utilize pipe-in-pipearrangements to transport fuel and oxidizer downhole, and then to removethe flue gas back up to the surface. Some downhole burners generate aflame, while others may not.

The use of downhole burners is an alternative to another form ofdownhole heat generation called steam generation. In downhole steamgeneration, a combustor in the well is used to boil water placed in thewellbore for injection into the formation. Applications of the downholeheat technology have been described in F. M. Smith, “A Down-holeburner—Versatile tool for well heating,” 25^(th) Technical Conference onPetroleum Production, Pennsylvania State University, pp 275-285 (Oct.19-21, 1966); H. Brandt, W. G. Poynter, and J. D. Hummell, “StimulatingHeavy Oil Reservoirs with Downhole Air-Gas Burners,” World Oil, pp.91-95 (September 1965); and C.I. DePriester and A. J. Pantaleo, “WellStimulation by Downhole Gas-Air Burner,” Journal of PetroleumTechnology, pp. 1297-1302 (December 1963).

Downhole burners have advantages over electrical heating methods due tothe reduced infrastructure cost. In this respect, there is no need foran expensive electrical power plant and distribution system. Moreover,there is increased thermal efficiency because the energy lossesinherently experienced during electrical power generation are avoided.

Few applications of downhole burners exist. Downhole burner designissues include temperature control and metallurgy limitations. In thisrespect, the flame temperature can overheat the tubular and burnerhardware and cause them to fail via melting, thermal stresses, severeloss of tensile strength, or creep. Certain stainless steels, typicallywith high chromium content, can tolerate temperatures up to ˜700° C. forextended periods. (See for example H. E. Boyer and T. L. Gall (eds.),Metals Handbook, “Chapter 16: Heat-Resistant Materials”, AmericanSociety for Metals, (1985.) The existence of flames can cause hot spotswithin the burner and in the formation surrounding the burner. This isdue to radiant heat transfer from the luminous portion of the flame.However, a typical gas flame can produce temperatures up to about 1,650°C. Materials of construction for the burners must be sufficient towithstand the temperatures of these hot spots. The heaters are thereforemore expensive than a comparable heater without flames.

For downhole burner applications, heat transfer can occur in one ofseveral ways. These include conduction, convection, and radiativemethods. Radiative heat transfer can be particularly strong for an openflame. Additionally, the flue gases can be corrosive due to the CO₂ andwater content. Use of refractory metals or ceramics can help solve theseproblems, but typically at a higher cost. Ceramic materials withacceptable strength at temperatures in excess of 900° C. are generallyhigh alumina content ceramics. Other ceramics that may be useful includechrome oxide, zirconia oxide, and magnesium oxide based ceramics.Additionally, depending on the nature of the downhole combustion NO_(x)generation may be significant.

Heat transfer in a pipe-in-pipe arrangement for a downhole burner canalso lead to difficulties. The down going fuel and air will heatexchange with the up going hot flue gases. In a well there is minimalroom for a high degree of insulation and hence significant heat transferis typically expected. This cross heat exchange can lead to higher flametemperatures as the fuel and air become preheated. Additionally, thecross heat exchange can limit the transport of heat downstream of theburner since the hot flue gases may rapidly lose heat energy to therising cooler flue gases.

In the production of oil and gas resources, it may be desirable to usethe produced hydrocarbons as a source of power for ongoing operations.This may be applied to the development of oil and gas resources from oilshale. In this respect, when electrically resistive heaters are used inconnection with in situ shale oil recovery, large amounts of power arerequired.

Electrical power may be obtained from turbines that turn generators. Itmay be economically advantageous to power the gas turbines by utilizingproduced gas from the field. However, such produced gas must becarefully controlled so not to damage the turbine, cause the turbine tomisfire, or generate excessive pollutants (e.g., NO_(x)).

One source of problems for gas turbines is the presence of contaminantswithin the fuel. Contaminants include solids, water, heavy componentspresent as liquids, and hydrogen sulfide. Additionally, the combustionbehavior of the fuel is important. Combustion parameters to considerinclude heating value, specific gravity, adiabatic flame temperature,flammability limits, autoignition temperature, autoignition delay time,and flame velocity. Wobbe Index (WI) is often used as a key measure offuel quality. WI is equal to the ratio of the lower heating value to thesquare root of the gas specific gravity. Control of the fuel's WobbeIndex to a target value and range of, for example, ±10% or ±20% canallow simplified turbine design and increased optimization ofperformance.

Fuel quality control may be useful for shale oil developments where theproduced gas composition may change over the life of the field and wherethe gas typically has significant amounts of CO₂, CO, and H₂ in additionto light hydrocarbons. Commercial scale oil shale retorting is expectedto produce a gas composition that changes with time.

Inert gases in the turbine fuel can increase power generation byincreasing mass flow while maintaining a flame temperature in adesirable range. Moreover inert gases can lower flame temperature andthus reduce NO_(x) pollutant generation. Gas generated from oil shalematuration may have significant CO₂ content. Therefore, in certainembodiments of the production processes, the CO₂ content of the fuel gasis adjusted via separation or addition in the surface facilities tooptimize turbine performance.

Achieving a certain hydrogen content for low-BTU fuels may also bedesirable to achieve appropriate burn properties. In certain embodimentsof the processes herein, the H₂ content of the fuel gas is adjusted viaseparation or addition in the surface facilities to optimize turbineperformance. Adjustment of H₂ content in non-shale oil surfacefacilities utilizing low BTU fuels has been discussed in the patentliterature (e.g., U.S. Pat. No. 6,684,644 and U.S. Pat. No. 6,858,049,the entire disclosures of which are hereby incorporated by reference).

The process of heating formation hydrocarbons within an organic-richrock formation, for example, by pyrolysis, may generate fluids. Theheat-generated fluids may include water which is vaporized within theformation. In addition, the action of heating kerogen produces pyrolysisfluids which tend to expand upon heating. The produced pyrolysis fluidsmay include not only water, but also, for example, hydrocarbons, oxidesof carbon, ammonia, molecular nitrogen, and molecular hydrogen.Therefore, as temperatures within a heated portion of the formationincrease, a pressure within the heated portion may also increase as aresult of increased fluid generation, molecular expansion, andvaporization of water. Thus, some corollary exists between subsurfacepressure in an oil shale formation and the fluid pressure generatedduring pyrolysis. This, in turn, indicates that formation pressure maybe monitored to detect the progress of a kerogen conversion process.

The pressure within a heated portion of an organic-rich rock formationdepends on other reservoir characteristics. These may include, forexample, formation depth, distance from a heater well, a richness of theformation hydrocarbons within the organic-rich rock formation, thedegree of heating, and/or a distance from a producer well.

It may be desirable for the developer of an oil shale field to monitorformation pressure during development. Pressure within a formation maybe determined at a number of different locations. Such locations mayinclude, but may not be limited to, at a wellhead and at varying depthswithin a wellbore. In some embodiments, pressure may be measured at aproducer well. In an alternate embodiment, pressure may be measured at aheater well. In still another embodiment, pressure may be measureddownhole of a dedicated monitoring well.

The process of heating an organic-rich rock formation to a pyrolysistemperature range not only will increase formation pressure, but willalso increase formation permeability. The pyrolysis temperature rangeshould be reached before substantial permeability has been generatedwithin the organic-rich rock formation. An initial lack of permeabilitymay prevent the transport of generated fluids from a pyrolysis zonewithin the formation. In this manner, as heat is initially transferredfrom a heater well to an organic-rich rock formation, a fluid pressurewithin the organic-rich rock formation may increase proximate to thatheater well. Such an increase in fluid pressure may be caused by, forexample, the generation of fluids during pyrolysis of at least someformation hydrocarbons in the formation.

Alternatively, pressure generated by expansion of pyrolysis fluids orother fluids generated in the formation may be allowed to increase. Thisassumes that an open path to a production well or other pressure sinkdoes not yet exist in the formation. In one aspect, a fluid pressure maybe allowed to increase to or above a lithostatic stress. In thisinstance, fractures in the hydrocarbon containing formation may formwhen the fluid pressure equals or exceeds the lithostatic stress. Forexample, fractures may form from a heater well to a production well. Thegeneration of fractures within the heated portion may reduce pressurewithin the portion due to the production of produced fluids through aproduction well.

Once pyrolysis has begun within an organic-rich rock formation, fluidpressure may vary depending upon various factors. These include, forexample, thermal expansion of hydrocarbons, generation of pyrolysisfluids, rate of conversion, and withdrawal of generated fluids from theformation. For example, as fluids are generated within the formation,fluid pressure within the pores may increase. Removal of generatedfluids from the formation may then decrease the fluid pressure withinthe near wellbore region of the formation.

In certain embodiments, a mass of at least a portion of an organic-richrock formation may be reduced due, for example, to pyrolysis offormation hydrocarbons and the production of hydrocarbon fluids from theformation. As such, the permeability and porosity of at least a portionof the formation may increase. Any in situ method that effectivelyproduces oil and gas from oil shale will create permeability in what wasoriginally a very low permeability rock. The extent to which this willoccur is illustrated by the large amount of expansion that must beaccommodated if fluids generated from kerogen are unable to flow. Theconcept is illustrated in FIG. 5.

FIG. 5 provides a bar chart comparing one ton of Green River oil shalebefore 50 and after 51 a simulated in situ, retorting process. Thesimulated process was carried out at 2,400 psi and 750° F. on oil shalehaving a total organic carbon content of 22 wt. % and a Fisher assay of42 gallons/ton. Before the conversion, a total of 15.3 ft³ of rockmatrix 52 existed. This matrix comprised 7.2 ft³ of mineral 53, i.e.,dolomite, limestone, etc., and 8.1 ft³ of kerogen 54 imbedded within theshale. As a result of the conversion the material expanded to 26.1 ft³55. This represented 7.2 ft³ of mineral 56 (the same number as beforethe conversion), 6.6 ft³ of hydrocarbon liquid 57, 9.4 ft³ ofhydrocarbon vapor 58, and 2.9 ft³ of coke 59. It can be seen thatsubstantial volume expansion occurred during the conversion process.This, in turn, increases permeability of the rock structure.

In an embodiment, heating a portion of an organic-rich rock formation insitu to a pyrolysis temperature may increase permeability of the heatedportion. For example, permeability may increase due to formation ofthermal fractures within the heated portion caused by application ofheat. As the temperature of the heated portion increases, water may beremoved due to vaporization. The vaporized water may escape and/or beremoved from the formation. In addition, permeability of the heatedportion may also increase as a result of production of hydrocarbonfluids from pyrolysis of at least some of the formation hydrocarbonswithin the heated portion on a macroscopic scale.

Certain systems and methods described herein may be used to treatformation hydrocarbons in at least a portion of a relatively lowpermeability formation (e.g., in “tight” formations that containformation hydrocarbons). Such formation hydrocarbons may be heated topyrolyze at least some of the formation hydrocarbons in a selected zoneof the formation. Heating may also increase the permeability of at leasta portion of the selected zone.

Hydrocarbon fluids generated from pyrolysis may be produced from theformation, thereby further increasing the formation permeability.

Permeability of a selected zone within the heated portion of theorganic-rich rock formation may also rapidly increase while the selectedzone is heated by conduction. For example, permeability of animpermeable organic-rich rock formation may be less than about 0.1millidarcy before heating. In some embodiments, pyrolyzing at least aportion of organic-rich rock formation may increase permeability withina selected zone of the portion to greater than about 10 millidarcies,100 millidarcies, 1 Darcy, 10 Darcies, 20 Darcies, or 50 Darcies.Therefore, a permeability of a selected zone of the portion may increaseby a factor of more than about 10, 100, 1,000, 10,000, or 100,000. Inone embodiment, the organic-rich rock formation has an initial totalpermeability less than 1 millidarcy, alternatively less than 0.1 or 0.01millidarcies, before heating the organic-rich rock formation. In oneembodiment, the organic-rich rock formation has a post heating totalpermeability of greater than 1 millidarcy, alternatively, greater than10, 50 or 100 millidarcies, after heating the organic-rich rockformation.

In connection with heating the organic-rich rock formation, theorganic-rich rock formation may optionally be fractured to aid heattransfer or hydrocarbon fluid production. In one instance, fracturingmay be accomplished naturally by creating thermal fractures within theformation through application of heat. Thermal fracture formation iscaused by thermal expansion of the rock and fluids and by chemicalexpansion of kerogen transforming into oil and gas. Thermal fracturingcan occur both in the immediate region undergoing heating, and in coolerneighboring regions. The thermal fracturing in the neighboring regionsis due to propagation of fractures and tension stresses developed due tothe expansion in the hotter zones. Thus, by both heating theorganic-rich rock and transforming the kerogen to oil and gas, thepermeability is increased not only from fluid formation andvaporization, but also via thermal fracture formation. The increasedpermeability aids fluid flow within the formation and production of thehydrocarbon fluids generated from the kerogen.

In addition, a process known as hydraulic fracturing may be used.Hydraulic fracturing is a process known in the art of oil and gasrecovery where a fracture fluid is pressurized within the wellbore abovethe fracture pressure of the formation, thus developing fracture planeswithin the formation to relieve the pressure generated within thewellbore. Hydraulic fractures may be used to create additionalpermeability and/or be used to provide an extended geometry for a heaterwell. The U.S. Pat. No. 7,331,385 patent publication incorporated abovedescribes one such method.

In connection with the production of hydrocarbons from a rock matrix,particularly those of shallow depth, a concern may exist with respect toearth subsidence. This is particularly true in the in situ heating oforganic-rich rock where a portion of the matrix itself is thermallyconverted and removed. Initially, the formation may contain formationhydrocarbons in solid form, such as, for example, kerogen. The formationmay also initially contain water-soluble minerals. Initially, theformation may also be substantially impermeable to fluid flow.

The in situ heating of the matrix pyrolyzes at least a portion of theformation hydrocarbons to create hydrocarbon fluids. This, in turn,creates permeability within a matured (pyrolyzed) organic-rich rock zonein the organic-rich rock formation. The combination of pyrolyzation andincreased permeability permits hydrocarbon fluids to be produced fromthe formation. At the same time, the loss of supporting matrix materialalso creates the potential for subsidence relative to the earth surface.

In some instances, subsidence is sought to be minimized in order toavoid environmental or hydrogeological impact. In this respect, changingthe contour and relief of the earth surface, even by a few inches, canchange runoff patterns, affect vegetation patterns, and impactwatersheds. In addition, subsidence has the potential of damagingproduction or heater wells formed in a production area. Such subsidencecan create damaging hoop and compressional stresses on wellbore casings,cement jobs, and equipment downhole.

In order to avoid or minimize subsidence, it is proposed to leaveselected portions of the formation hydrocarbons substantiallyunpyrolyzed. This serves to preserve one or more unmatured, organic-richrock zones. In some embodiments, the unmatured organic-rich rock zonesmay be shaped as substantially vertical pillars extending through asubstantial portion of the thickness of the organic-rich rock formation.

The heating rate and distribution of heat within the formation may bedesigned and implemented to leave sufficient unmatured pillars toprevent subsidence. In one aspect, heat injection wellbores are formedin a pattern such that untreated pillars of oil shale are lefttherebetween to support the overburden and prevent subsidence.

It is preferred that thermal recovery of oil and gas be conducted beforeany solution mining of nahcolite or other water-soluble minerals presentin the formation. Solution mining can generate large voids in a rockformation and collapse breccias in an oil shale development area. Thesevoids and brecciated zones may pose problems for in situ and miningrecovery of oil shale, further increasing the utility of supportingpillars.

In some embodiments, compositions and properties of the hydrocarbonfluids produced by an in situ conversion process may vary depending on,for example, conditions within an organic-rich rock formation.Controlling heat and/or heating rates of a selected section in anorganic-rich rock formation may increase or decrease production ofselected produced fluids.

In one embodiment, operating conditions may be determined by measuringat least one property of the organic-rich rock formation. The measuredproperties may be input into a computer executable program. At least oneproperty of the produced fluids selected to be produced from theformation may also be input into the computer executable program. Theprogram may be operable to determine a set of operating conditions fromat least the one or more measured properties. The program may also beconfigured to determine the set of operating conditions from at leastone property of the selected produced fluids. In this manner, thedetermined set of operating conditions may be configured to increaseproduction of selected produced fluids from the formation.

Certain heater well embodiments may include an operating system that iscoupled to any of the heater wells such as by insulated conductors orother types of wiring. The operating system may be configured tointerface with the heater well. The operating system may receive asignal (e.g., an electromagnetic signal) from a heater that isrepresentative of a temperature distribution of the heater well.Additionally, the operating system may be further configured to controlthe heater well, either locally or remotely. For example, the operatingsystem may alter a temperature of the heater well by altering aparameter of equipment coupled to the heater well. Therefore, theoperating system may monitor, alter, and/or control the heating of atleast a portion of the formation.

In some embodiments, a heater well may be turned down and/or off afteran average temperature in a formation may have reached a selectedtemperature. Turning down and/or off the heater well may reduce inputenergy costs, substantially inhibit overheating of the formation, andallow heat to substantially transfer into colder regions of theformation.

Temperature (and average temperatures) within a heated organic-rich rockformation may vary, depending on, for example, proximity to a heaterwell, thermal conductivity and thermal diffusivity of the formation,type of reaction occurring, type of formation hydrocarbon, and thepresence of water within the organic-rich rock formation. At points inthe field where monitoring wells are established, temperaturemeasurements may be taken directly in the wellbore. Further, at heaterwells the temperature of the immediately surrounding formation is fairlywell understood. However, it is desirable to interpolate temperatures topoints in the formation intermediate temperature sensors and heaterwells.

In accordance with one aspect of the production processes of the presentinventions, a temperature distribution within the organic-rich rockformation may be computed using a numerical simulation model. Thenumerical simulation model may calculate a subsurface temperaturedistribution through interpolation of known data points and assumptionsof formation conductivity. In addition, the numerical simulation modelmay be used to determine other properties of the formation under theassessed temperature distribution. For example, the various propertiesof the formation may include, but are not limited to, permeability ofthe formation.

The numerical simulation model may also include assessing variousproperties of a fluid formed within an organic-rich rock formation underthe assessed temperature distribution. For example, the variousproperties of a formed fluid may include, but are not limited to, acumulative volume of a fluid formed in the formation, fluid viscosity,fluid density, and a composition of the fluid formed in the formation.Such a simulation may be used to assess the performance of acommercial-scale operation or small-scale field experiment. For example,a performance of a commercial-scale development may be assessed basedon, but not limited to, a total volume of product that may be producedfrom a research-scale operation.

Some embodiments include producing at least a portion of the hydrocarbonfluids from the organic-rich rock formation. The hydrocarbon fluids maybe produced through production wells. Production wells may be cased oruncased wells and drilled and completed through methods known in theart.

Some embodiments further include producing a production fluid from theorganic-rich rock formation where the production fluid contains thehydrocarbon fluids and an aqueous fluid. The aqueous fluid may containwater-soluble minerals and/or migratory contaminant species. In suchcase, the production fluid may be separated into a hydrocarbon streamand an aqueous stream at a surface facility. Thereafter thewater-soluble minerals and/or migratory contaminant species may berecovered from the aqueous stream. This embodiment may be combined withany of the other aspects of the invention discussed herein.

The produced hydrocarbon fluids may include a pyrolysis oil component(or condensable component) and a pyrolysis gas component (ornon-condensable component). Condensable hydrocarbons produced from theformation will typically include paraffins, cycloalkanes,mono-aromatics, and di-aromatics as components. Such condensablehydrocarbons may also include other components such as tri-aromatics andother hydrocarbon species.

In certain embodiments, a majority of the hydrocarbons in the producedfluid may have a carbon number of less than approximately 25.Alternatively, less than about 15 weight % of the hydrocarbons in thefluid may have a carbon number greater than approximately 25. Thenon-condensable hydrocarbons may include, but are not limited to,hydrocarbons having carbon numbers less than 5.

In certain embodiments, the API gravity of the condensable hydrocarbonsin the produced fluid may be approximately 20 or above (e.g., 25, 30,40, 50, etc.). In certain embodiments, the hydrogen to carbon atomicratio in produced fluid may be at least approximately 1.7 (e.g., 1.8,1.9, etc.).

One embodiment of the invention includes an in situ method of producinghydrocarbon fluids with improved properties from an organic-rich rockformation. Applicants have surprisingly discovered that the quality ofthe hydrocarbon fluids produced from in situ heating and pyrolysis of anorganic-rich rock formation may be improved by selecting sections of theorganic-rich rock formation with higher lithostatic stress for in situheating and pyrolysis.

The method may include in situ heating of a section of the organic-richrock formation that has a high lithostatic stress to form hydrocarbonfluids with improved properties. The method may include creating thehydrocarbon fluid by pyrolysis of a solid hydrocarbon and/or a heavyhydrocarbon present in the organic-rich rock formation. Embodiments mayinclude the hydrocarbon fluid being partially, predominantly orsubstantially completely created by pyrolysis of the solid hydrocarbonand/or heavy hydrocarbon present in the organic-rich rock formation. Themethod may include heating the section of the organic-rich rockformation by any method, including any of the methods described herein.For example, the method may include heating the section of theorganic-rich rock formation by electrical resistance heating. Further,the method may include heating the section of the organic-rich rockformation through use of a heated heat transfer fluid. The method mayinclude heating the section of the organic-rich rock formation to above270° C. Alternatively, the method may include heating the section of theorganic-rich rock formation between 270° C. and 500° C.

The method may include heating in situ a section of the organic-richrock formation having a lithostatic stress greater than 200 psi andproducing a hydrocarbon fluid from the heated section of theorganic-rich rock formation. In alternative embodiments, the heatedsection of the organic-rich rock formation may have a lithostatic stressgreater than 400 psi. In alternative embodiments, the heated section ofthe organic-rich rock formation may have a lithostatic stress greaterthan 800 psi, greater than 1,000 psi, greater than 1,200 psi, greaterthan 1,500 psi or greater than 2,000 psi. Applicants have found that insitu heating and pyrolysis of organic-rich rock formations withincreasing amounts of stress lead to the production of hydrocarbonfluids with improved properties.

The lithostatic stress of a section of an organic-rich formation cannormally be estimated by recognizing that it will generally be equal tothe weight of the rocks overlying the formation. The density of theoverlying rocks can be expressed in units of psi/ft. Generally, thisvalue will fall between 0.8 and 1.1 psi/ft and can often be approximatedas 0.9 psi/ft. As a result the lithostatic stress of a section of anorganic-rich formation can be estimated by multiplying the depth of theorganic-rich rock formation interval by 0.9 psi/ft. Thus the lithostaticstress of a section of an organic-rich formation occurring at about1,000 ft can be estimated to be about (0.9 psi/ft) multiplied by (1,000ft) or about 900 psi. If a more precise estimate of lithostatic stressis desired the density of overlying rocks can be measured using wirelinelogging techniques or by making laboratory measurements on samplesrecovered from coreholes. The method may include heating a section ofthe organic-rich rock formation that is located at a depth greater than200 ft below the earth's surface. Alternatively, the method may includeheating a section of the organic-rich rock formation that is located ata depth greater than 500 ft below the earth's surface, greater than1,000 ft below the earth's surface, greater than 1,200 ft below theearth's surface, greater than 1,500 ft below the earth's surface, orgreater than 2,000 ft below the earth's surface.

The organic-rich rock formation may be, for example, a heavy hydrocarbonformation or a solid hydrocarbon formation. Particular examples of suchformations may include an oil shale formation, a tar sands formation ora coal formation. Particular formation hydrocarbons present in suchformations may include oil shale, kerogen, coal, and/or bitumen.

The hydrocarbon fluid produced from the organic-rich rock formation mayinclude both a condensable hydrocarbon portion (e.g. liquid) and anon-condensable hydrocarbon portion (e.g. gas). The hydrocarbon fluidmay additionally be produced together with non-hydrocarbon fluids.Exemplary non-hydrocarbon fluids include, for example, water, carbondioxide, hydrogen sulfide, hydrogen, ammonia, and/or carbon monoxide.

The condensable hydrocarbon portion of the hydrocarbon fluid may be afluid present within different locations associated with an organic-richrock development project. For example, the condensable hydrocarbonportion of the hydrocarbon fluid may be a fluid present within aproduction well that is in fluid communication with the organic-richrock formation. The production well may serve as a device forwithdrawing the produced hydrocarbon fluids from the organic-rich rockformation. Alternatively, the condensable hydrocarbon portion may be afluid present within processing equipment adapted to process hydrocarbonfluids produced from the organic-rich rock formation. Exemplaryprocessing equipment is described herein. Alternatively, the condensablehydrocarbon portion may be a fluid present within a fluid storagevessel. Fluid storage vessels may include, for example, fluid storagetanks with fixed or floating roofs, knock-out vessels, and otherintermediate, temporary or product storage vessels. Alternatively, thecondensable hydrocarbon portion may be a fluid present within a fluidtransportation pipeline. A fluid transportation pipeline may include,for example, piping from production wells to processing equipment orfluid storage vessels, piping from processing equipment to fluid storagevessels, or pipelines associated with collection or transportation offluids to or from intermediate or centralized storage locations.

The following discussion of FIGS. 7-16 concerns data obtained inExamples 1-5 which are discussed in the section labeled “Experiments”.The data was obtained through the experimental procedures, gas andliquid sample collection procedures, hydrocarbon gas sample gaschromatography (GC) analysis methodology, gas sample GC peak integrationmethodology, gas sample GC peak identification methodology, whole oilgas chromatography (WOGC) analysis methodology, whole oil gaschromatography (WOGC) peak integration methodology, whole oil gaschromatography (WOGC) peak identification methodology, and pseudocomponent analysis methodology discussed in the Experiments section. Forclarity, when referring to gas chromatography chromatograms ofhydrocarbon gas samples, graphical data is provided for one unstressedexperiment through Example 1, two 400 psi stressed experiments throughExamples 2 and 3, and two 1,000 psi stressed experiments throughExamples 4 and 5. When referring to whole oil gas chromatography (WOGC)chromatograms of liquid hydrocarbon samples, graphical data is providedfor one unstressed experiment through Example 1, one 400 psi stressedexperiments through Example 3, and one 1,000 psi stressed experimentthrough Example 4.

FIG. 7 is a graph of the weight percent of each carbon number pseudocomponent occurring from C6 to C38 for each of the three stress levelstested and analyzed in the laboratory experiments discussed herein. Thepseudo component weight percentages were obtained through theexperimental procedures, liquid sample collection procedures, whole oilgas chromatography (WOGC) analysis methodology, whole oil gaschromatography (WOGC) peak identification and integration methodology,and pseudo component analysis methodology discussed in the Experimentssection. For clarity, the pseudo component weight percentages are takenas a percentage of the entire C3 to pseudo C38 whole oil gaschromatography areas and calculated weights. Thus the graphed C6 to C38weight percentages do not include the weight contribution of theassociated gas phase product from any of the experiments which wasseparately treated. Further, the graphed weight percentages do notinclude the weight contribution of any liquid hydrocarbon compoundsheavier than (i.e. having a longer retention time than) the C38 pseudocomponent. The y-axis 2000 represents the concentration in terms ofweight percent of each C6 to C38 pseudo component in the liquid phase.The x-axis 2001 contains the identity of each hydrocarbon pseudocomponent from C6 to C38. The data points occurring on line 2002represent the weight percent of each C6 to C38 pseudo component for theunstressed experiment of Example 1. The data points occurring on line2003 represent the weight percent of each C6 to C38 pseudo component forthe 400 psi stressed experiment of Example 3. While the data pointsoccurring on line 2004 represent the weight percent of each C6 to C38pseudo component for the 1,000 psi stressed experiment of Example 4.From FIG. 7 it can be seen that the hydrocarbon liquid produced in theunstressed experiment, represented by data points on line 2002, containsa lower weight percentage of lighter hydrocarbon components in the C8 toC17 pseudo component range and a greater weight percentage of heavierhydrocarbon components in the C20 to C29 pseudo component range, both ascompared to the 400 psi stress experiment hydrocarbon liquid and the1,000 psi stress experiment hydrocarbon liquid. Looking now at the datapoints occurring on line 2003, it is apparent that the intermediatelevel 400 psi stress experiment produced a hydrocarbon liquid having C8to C17 pseudo component concentrations between the unstressed experimentrepresented by line 2002 and the 1,000 psi stressed experimentrepresented by line 2004. It is noted that the C17 pseudo component datafor both the 400 psi and 1,000 psi stressed experiments are about equal.Further, it is apparent that the weight percentage of heavierhydrocarbon components in the C20 to C29 pseudo component range for theintermediate stress level experiment represented by line 2003 fallsbetween the unstressed experiment (Line 2002) hydrocarbon liquid and the1,000 psi stress experiment (Line 2004) hydrocarbon liquid. Lastly, itis apparent that the high level 1,000 psi stress experiment produced ahydrocarbon liquid having C8 to C17 pseudo component concentrationsgreater than both the unstressed experiment represented by line 2002 andthe 400 psi stressed experiment represented by line 2003. Further, it isapparent that the weight percentage of heavier hydrocarbon components inthe C20 to C29 pseudo component range for the high level stressexperiment represented by line 2004 are less than both the unstressedexperiment (Line 2002) hydrocarbon liquid and the 400 psi stressexperiment (Line 2003) hydrocarbon liquid. Thus pyrolyzing oil shaleunder increasing levels of lithostatic stress appears to producehydrocarbon liquids having increasingly lighter carbon numberdistributions.

FIG. 8 is a graph of the weight percent ratios of each carbon numberpseudo component occurring from C6 to C38 as compared to the C20 pseudocomponent for each of the three stress levels tested and analyzed in thelaboratory experiments discussed herein. The pseudo component weightpercentages were obtained as described for FIG. 7. The y-axis 2020represents the weight ratio of each C6 to C38 pseudo component comparedto the C20 pseudo component in the liquid phase. The x-axis 2021contains the identity of each hydrocarbon pseudo component ratio fromC6/C20 to C38/C20. The data points occurring on line 2022 represent theweight ratio of each C6 to C38 pseudo component to C20 pseudo componentfor the unstressed experiment of Example 1. The data points occurring online 2023 represent the weight ratio of each C6 to C38 pseudo componentto C20 pseudo component for the 400 psi stressed experiment of Example3. While the data points occurring on line 2024 represent the weightratio of each C6 to C38 pseudo component to C20 pseudo component for the1,000 psi stressed experiment of Example 4. From FIG. 8 it can be seenthat the hydrocarbon liquid produced in the unstressed experiment,represented by data points on line 2022, contains a lower weightpercentage of lighter hydrocarbon components in the C8 to C18 pseudocomponent range as compared to the C20 pseudo component and a greaterweight percentage of heavier hydrocarbon components in the C22 to C29pseudo component range as compared to the C20 pseudo component, both ascompared to the 400 psi stress experiment hydrocarbon liquid and the1,000 psi stress experiment hydrocarbon liquid. Looking now at the datapoints occurring on line 2023, it is apparent that the intermediatelevel 400 psi stress experiment produced a hydrocarbon liquid having C8to C18 pseudo component concentrations as compared to the C20 pseudocomponent between the unstressed experiment represented by line 2022 andthe 1,000 psi stressed experiment represented by line 2024. Further, itis apparent that the weight percentage of heavier hydrocarbon componentsin the C22 to C29 pseudo component range as compared to the C20 pseudocomponent for the intermediate stress level experiment represented byline 2023 falls between the unstressed experiment (Line 2022)hydrocarbon liquid and the 1,000 psi stress experiment (Line 2024)hydrocarbon liquid. Lastly, it is apparent that the high level 1,000 psistress experiment produced a hydrocarbon liquid having C8 to C18 pseudocomponent concentrations as compared to the C20 pseudo component greaterthan both the unstressed experiment represented by line 2022 and the 400psi stressed experiment represented by line 2023. Further, it isapparent that the weight percentage of heavier hydrocarbon components inthe C22 to C29 pseudo component range as compared to the C20 pseudocomponent for the high level stress experiment represented by line 2024are less than both the unstressed experiment (Line 2022) hydrocarbonliquid and the 400 psi stress experiment (Line 2023) hydrocarbon liquid.This analysis further supports the relationship that pyrolizing oilshale under increasing levels of lithostatic stress produces hydrocarbonliquids having increasingly lighter carbon number distributions.

FIG. 9 is a graph of the weight percent ratios of each carbon numberpseudo component occurring from C6 to C38 as compared to the C25 pseudocomponent for each of the three stress levels tested and analyzed in thelaboratory experiments discussed herein. The pseudo component weightpercentages were obtained as described for FIG. 7. The y-axis 2040represents the weight ratio of each C6 to C38 pseudo component comparedto the C25 pseudo component in the liquid phase. The x-axis 2041contains the identity of each hydrocarbon pseudo component ratio fromC6/C25 to C38/C25. The data points occurring on line 2042 represent theweight ratio of each C6 to C38 pseudo component to C25 pseudo componentfor the unstressed experiment of Example 1. The data points occurring online 2043 represent the weight ratio of each C6 to C38 pseudo componentto C25 pseudo component for the 400 psi stressed experiment of Example3. While the data points occurring on line 2044 represent the weightratio of each C6 to C38 pseudo component to C25 pseudo component for the1,000 psi stressed experiment of Example 4. From FIG. 9 it can be seenthat the hydrocarbon liquid produced in the unstressed experiment,represented by data points on line 2042, contains a lower weightpercentage of lighter hydrocarbon components in the C7 to C24 pseudocomponent range as compared to the C25 pseudo component and a greaterweight percentage of heavier hydrocarbon components in the C26 to C29pseudo component range as compared to the C25 pseudo component, both ascompared to the 400 psi stress experiment hydrocarbon liquid and the1,000 psi stress experiment hydrocarbon liquid. Looking now at the datapoints occurring on line 2043, it is apparent that the intermediatelevel 400 psi stress experiment produced a hydrocarbon liquid having C7to C24 pseudo component concentrations as compared to the C25 pseudocomponent between the unstressed experiment represented by line 2042 andthe 1,000 psi stressed experiment represented by line 2044. Further, itis apparent that the weight percentage of heavier hydrocarbon componentsin the C26 to C29 pseudo component range as compared to the C25 pseudocomponent for the intermediate stress level experiment represented byline 2043 falls between the unstressed experiment (Line 2042)hydrocarbon liquid and the 1,000 psi stress experiment (Line 2044)hydrocarbon liquid. Lastly, it is apparent that the high level 1,000 psistress experiment produced a hydrocarbon liquid having C7 to C24 pseudocomponent concentrations as compared to the C25 pseudo component greaterthan both the unstressed experiment represented by line 2042 and the 400psi stressed experiment represented by line 2043. Further, it isapparent that the weight percentage of heavier hydrocarbon components inthe C26 to C29 pseudo component range as compared to the C25 pseudocomponent for the high level stress experiment represented by line 2044are less than both the unstressed experiment (Line 2042) hydrocarbonliquid and the 400 psi stress experiment (Line 2043) hydrocarbon liquid.This analysis further supports the relationship that pyrolizing oilshale under increasing levels of lithostatic stress produces hydrocarbonliquids having increasingly lighter carbon number distributions.

FIG. 10 is a graph of the weight percent ratios of each carbon numberpseudo component occurring from C6 to C38 as compared to the C29 pseudocomponent for each of the three stress levels tested and analyzed in thelaboratory experiments discussed herein. The pseudo component weightpercentages were obtained as described for FIG. 7. The y-axis 2060represents the weight ratio of each C6 to C38 pseudo component comparedto the C29 pseudo component in the liquid phase. The x-axis 2061contains the identity of each hydrocarbon pseudo component ratio fromC6/C29 to C38/C29. The data points occurring on line 2062 represent theweight ratio of each C6 to C38 pseudo component to C29 pseudo componentfor the unstressed experiment of Example 1. The data points occurring online 2063 represent the weight ratio of each C6 to C38 pseudo componentto C29 pseudo component for the 400 psi stressed experiment of Example3. While the data points occurring on line 2064 represent the weightratio of each C6 to C38 pseudo component to C29 pseudo component for the1,000 psi stressed experiment of Example 4. From FIG. 10 it can be seenthat the hydrocarbon liquid produced in the unstressed experiment,represented by data points on line 2062, contains a lower weightpercentage of lighter hydrocarbon components in the C6 to C28 pseudocomponent range as compared to the C29 pseudo component, both ascompared to the 400 psi stress experiment hydrocarbon liquid and the1,000 psi stress experiment hydrocarbon liquid. Looking now at the datapoints occurring on line 2063, it is apparent that the intermediatelevel 400 psi stress experiment produced a hydrocarbon liquid having C6to C28 pseudo component concentrations as compared to the C29 pseudocomponent between the unstressed experiment represented by line 2062 andthe 1,000 psi stressed experiment represented by line 2064. Lastly, itis apparent that the high level 1,000 psi stress experiment produced ahydrocarbon liquid having C6 to C28 pseudo component concentrations ascompared to the C29 pseudo component greater than both the unstressedexperiment represented by line 2062 and the 400 psi stressed experimentrepresented by line 2063. This analysis further supports therelationship that pyrolizing oil shale under increasing levels oflithostatic stress produces hydrocarbon liquids having increasinglylighter carbon number distributions.

FIG. 11 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from the normal-C6 alkane to the normal-C38 alkanefor each of the three stress levels tested and analyzed in thelaboratory experiments discussed herein. The normal alkane compoundweight percentages were obtained as described for FIG. 7, except thateach individual normal alkane compound peak area integration was used todetermine each respective normal alkane compound weight percentage. Forclarity, the normal alkane hydrocarbon weight percentages are taken as apercentage of the entire C3 to pseudo C38 whole oil gas chromatographyareas and calculated weights as used in the pseudo compound datapresented in FIG. 7. The y-axis 2080 represents the concentration interms of weight percent of each normal-C6 to normal-C38 compound foundin the liquid phase. The x-axis 2081 contains the identity of eachnormal alkane hydrocarbon compound from normal-C6 to normal-C38. Thedata points occurring on line 2082 represent the weight percent of eachnormal-C6 to normal-C38 hydrocarbon compound for the unstressedexperiment of Example 1. The data points occurring on line 2083represent the weight percent of each normal-C6 to normal-C38 hydrocarboncompound for the 400 psi stressed experiment of Example 3. While thedata points occurring on line 2084 represent the weight percent of eachnormal-C6 to normal-C38 hydrocarbon compound for the 1,000 psi stressedexperiment of Example 4. From FIG. 11 it can be seen that thehydrocarbon liquid produced in the unstressed experiment, represented bydata points on line 2082, contains a greater weight percentage ofhydrocarbon compounds in the normal-C12 to normal-C30 compound range,both as compared to the 400 psi stress experiment hydrocarbon liquid andthe 1,000 psi stress experiment hydrocarbon liquid. Looking now at thedata points occurring on line 2083, it is apparent that the intermediatelevel 400 psi stress experiment produced a hydrocarbon liquid havingnormal-C12 to normal-C30 compound concentrations between the unstressedexperiment represented by line 2082 and the 1,000 psi stressedexperiment represented by line 2084. Lastly, it is apparent that thehigh level 1,000 psi stress experiment produced a hydrocarbon liquidhaving normal-C12 to normal-C30 compound concentrations less than boththe unstressed experiment represented by line 2082 and the 400 psistressed experiment represented by line 2083. Thus pyrolyzing oil shaleunder increasing levels of lithostatic stress appears to producehydrocarbon liquids having lower concentrations of normal alkanehydrocarbons.

FIG. 12 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from normal-C6 to normal-C38 as compared to thenormal-C20 hydrocarbon compound for each of the three stress levelstested and analyzed in the laboratory experiments discussed herein. Thenormal compound weight percentages were obtained as described for FIG.11. The y-axis 3000 represents the concentration in terms of weightratio of each normal-C6 to normal-C38 compound as compared to thenormal-C20 compound found in the liquid phase. The x-axis 3001 containsthe identity of each normal alkane hydrocarbon compound ratio fromnormal-C6/normal-C20 to normal-C38/normal-C20. The data points occurringon line 3002 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C20 compound for theunstressed experiment of Example 1. The data points occurring on line3003 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C20 compound for the 400psi stressed experiment of Example 3. While the data points occurring online 3004 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C20 compound for the1,000 psi stressed experiment of Example 4. From FIG. 12 it can be seenthat the hydrocarbon liquid produced in the unstressed experiment,represented by data points on line 3002, contains a lower weightpercentage of lighter normal alkane hydrocarbon components in thenormal-C6 to normal-C17 compound range as compared to the normal-C20compound and a greater weight percentage of heavier hydrocarboncomponents in the normal-C22 to normal-C34 compound range as compared tothe normal-C20 compound, both as compared to the 400 psi stressexperiment hydrocarbon liquid and the 1,000 psi stress experimenthydrocarbon liquid. Looking now at the data points occurring on line3003, it is apparent that the intermediate level 400 psi stressexperiment produced a hydrocarbon liquid having normal-C6 to normal-C17compound concentrations as compared to the normal-C20 compound betweenthe unstressed experiment represented by line 3002 and the 1,000 psistressed experiment represented by line 3004. Further, it is apparentthat the weight percentage of heavier hydrocarbon components in thenormal-C22 to normal-C34 compound range as compared to the normal-C20compound for the intermediate stress level experiment represented byline 3003 falls between the unstressed experiment (Line 3002)hydrocarbon liquid and the 1,000 psi stress experiment (Line 3004)hydrocarbon liquid. Lastly, it is apparent that the high level 1,000 psistress experiment produced a hydrocarbon liquid having normal-C6 tonormal-C17 compound concentrations as compared to the normal-C20compound greater than both the unstressed experiment represented by line3002 and the 400 psi stressed experiment represented by line 3003.Further, it is apparent that the weight percentage of heavierhydrocarbon components in the normal-C22 to normal-C34 compound range ascompared to the normal-C20 compound for the high level stress experimentrepresented by line 3004 are less than both the unstressed experiment(Line 3002) hydrocarbon liquid and the 400 psi stress experiment (Line3003) hydrocarbon liquid. This analysis further supports therelationship that pyrolizing oil shale under increasing levels oflithostatic stress produces hydrocarbon liquids having lowerconcentrations of normal alkane hydrocarbons.

FIG. 13 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from normal-C6 to normal-C38 as compared to thenormal-C25 hydrocarbon compound for each of the three stress levelstested and analyzed in the laboratory experiments discussed herein. Thenormal compound weight percentages were obtained as described for FIG.11. The y-axis 3020 represents the concentration in terms of weightratio of each normal-C6 to normal-C38 compound as compared to thenormal-C25 compound found in the liquid phase. The x-axis 3021 containsthe identity of each normal alkane hydrocarbon compound ratio fromnormal-C6/normal-C25 to normal-C38/normal-C25. The data points occurringon line 3022 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C25 compound for theunstressed experiment of Example 1. The data points occurring on line3023 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C25 compound for the 400psi stressed experiment of Example 3. While the data points occurring online 3024 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C25 compound for the1,000 psi stressed experiment of Example 4. From FIG. 13 it can be seenthat the hydrocarbon liquid produced in the unstressed experiment,represented by data points on line 3022, contains a lower weightpercentage of lighter normal alkane hydrocarbon components in thenormal-C6 to normal-C24 compound range as compared to the normal-C25compound and a greater weight percentage of heavier hydrocarboncomponents in the normal-C26 to normal-C30 compound range as compared tothe normal-C25 compound, both as compared to the 400 psi stressexperiment hydrocarbon liquid and the 1,000 psi stress experimenthydrocarbon liquid. Looking now at the data points occurring on line3023, it is apparent that the intermediate level 400 psi stressexperiment produced a hydrocarbon liquid having normal-C6 to normal-C24compound concentrations as compared to the normal-C25 compound betweenthe unstressed experiment represented by line 3022 and the 1,000 psistressed experiment represented by line 3024. Further, it is apparentthat the weight percentage of heavier hydrocarbon components in thenormal-C26 to normal-C30 compound range as compared to the normal-C25compound for the intermediate stress level experiment represented byline 3023 falls between the unstressed experiment (Line 3022)hydrocarbon liquid and the 1,000 psi stress experiment (Line 3024)hydrocarbon liquid. Lastly, it is apparent that the high level 1,000 psistress experiment produced a hydrocarbon liquid having normal-C6 tonormal-C24 compound concentrations as compared to the normal-C25compound greater than both the unstressed experiment represented by line3022 and the 400 psi stressed experiment represented by line 3023.Further, it is apparent that the weight percentage of heavierhydrocarbon components in the normal-C26 to normal-C30 compound range ascompared to the normal-C25 compound for the high level stress experimentrepresented by line 3024 are less than both the unstressed experiment(Line 3022) hydrocarbon liquid and the 400 psi stress experiment (Line3023) hydrocarbon liquid. This analysis further supports therelationship that pyrolizing oil shale under increasing levels oflithostatic stress produces hydrocarbon liquids having lowerconcentrations of normal alkane hydrocarbons.

FIG. 14 is a graph of the weight percent of normal alkane hydrocarboncompounds occurring from normal-C6 to normal-C38 as compared to thenormal-C29 hydrocarbon compound for each of the three stress levelstested and analyzed in the laboratory experiments discussed herein. Thenormal compound weight percentages were obtained as described for FIG.11. The y-axis 3040 represents the concentration in terms of weightratio of each normal-C6 to normal-C38 compound as compared to thenormal-C29 compound found in the liquid phase. The x-axis 3041 containsthe identity of each normal alkane hydrocarbon compound ratio fromnormal-C6/normal-C29 to normal-C38/normal-C29. The data points occurringon line 3042 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C29 compound for theunstressed experiment of Example 1. The data points occurring on line3043 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C29 compound for the 400psi stressed experiment of Example 3. While the data points occurring online 3044 represent the weight ratio of each normal-C6 to normal-C38hydrocarbon compound as compared to the normal-C29 compound for the1,000 psi stressed experiment of Example 4. From FIG. 14 it can be seenthat the hydrocarbon liquid produced in the unstressed experiment,represented by data points on line 3042, contains a lower weightpercentage of lighter normal alkane hydrocarbon components in thenormal-C6 to normal-C26 compound range as compared to the normal-C29compound, both as compared to the 400 psi stress experiment hydrocarbonliquid and the 1,000 psi stress experiment hydrocarbon liquid. Lookingnow at the data points occurring on line 3043, it is apparent that theintermediate level 400 psi stress experiment produced a hydrocarbonliquid having normal-C6 to normal-C26 compound concentrations ascompared to the normal-C29 compound between the unstressed experimentrepresented by line 3042 and the 1,000 psi stressed experimentrepresented by line 3044. Lastly, it is apparent that the high level1,000 psi stress experiment produced a hydrocarbon liquid havingnormal-C6 to normal-C26 compound concentrations as compared to thenormal-C29 compound greater than both the unstressed experimentrepresented by line 3042 and the 400 psi stressed experiment representedby line 3043. This analysis further supports the relationship thatpyrolizing oil shale under increasing levels of lithostatic stressproduces hydrocarbon liquids having lower concentrations of normalalkane hydrocarbons.

FIG. 15 is a graph of the weight ratio of normal alkane hydrocarboncompounds to pseudo components for each carbon number from C6 to C38 foreach of the three stress levels tested and analyzed in the laboratoryexperiments discussed herein. The normal compound and pseudo componentweight percentages were obtained as described for FIGS. 7 & 11. Forclarity, the normal alkane hydrocarbon and pseudo component weightpercentages are taken as a percentage of the entire C3 to pseudo C38whole oil gas chromatography areas and calculated weights as used in thepseudo compound data presented in FIG. 7. The y-axis 3060 represents theconcentration in terms of weight ratio of each normal-C6/pseudo C6 tonormal-C38/pseudo C38 compound found in the liquid phase. The x-axis3061 contains the identity of each normal alkane hydrocarbon compound topseudo component ratio from normal-C6/pseudo C6 to normal-C38/pseudoC38. The data points occurring on line 3062 represent the weight ratioof each normal-C6/pseudo C6 to normal-C38/pseudo C38 ratio for theunstressed experiment of Example 1. The data points occurring on line3063 represent the weight ratio of each normal-C6/pseudo C6 tonormal-C38/pseudo C38 ratio for the 400 psi stressed experiment ofExample 3. While the data points occurring on line 3064 represent theweight ratio of each normal-C6/pseudo C6 to normal-C38/pseudo C38 ratiofor the 1,000 psi stressed experiment of Example 4. From FIG. 15 it canbe seen that the hydrocarbon liquid produced in the unstressedexperiment, represented by data points on line 3062, contains a greaterweight percentage of normal alkane hydrocarbon compounds to pseudocomponents in the C10 to C26 range, both as compared to the 400 psistress experiment hydrocarbon liquid and the 1,000 psi stress experimenthydrocarbon liquid. Looking now at the data points occurring on line3063, it is apparent that the intermediate level 400 psi stressexperiment produced a hydrocarbon liquid having normal alkanehydrocarbon compound to pseudo component ratios in the C10 to C26 rangebetween the unstressed experiment represented by line 3062 and the 1,000psi stressed experiment represented by line 3064. Lastly, it is apparentthat the high level 1,000 psi stress experiment produced a hydrocarbonliquid having normal alkane hydrocarbon compound to pseudo componentratios in the C10 to C26 range less than both the unstressed experimentrepresented by line 3062 and the 400 psi stressed experiment representedby line 3063. Thus pyrolizing oil shale under increasing levels oflithostatic stress appears to produce hydrocarbon liquids having lowerconcentrations of normal alkane hydrocarbons as compared to the totalhydrocarbons for a given carbon number occurring between C10 and C26.

The following discussion of FIGS. 60-61 concerns data obtained inExamples 6-19 which are discussed in the section labeled “Experiments”.The data was obtained through the experimental procedures, gas andliquid sample collection procedures, whole oil gas chromatography (WOGC)analysis methodology, whole oil gas chromatography (WOGC) peakintegration methodology, whole oil gas chromatography (WOGC) peakidentification methodology, and analysis methodology discussed in theExperiments section.

FIG. 60 is a graph of the weight ratio of each WOGC identified compoundoccurring from i-C4 to n-C35 for each of the six 393° C. experimentstested and analyzed by WOGC in the laboratory experiments (Examples13-19) discussed herein compared to the weight ratio of each identifiedcompound occurring from i-C4 to n-C35 for Example 13 conducted at 393°C., 500 psig initial argon pressure and 0 psi stress. The compoundweight ratios were obtained through the experimental procedures, liquidsample collection procedures, whole oil gas chromatography (WOGC)analysis methodology, whole oil gas chromatography (WOGC) peakintegration methodology, and whole oil gas chromatography (WOGC) peakidentification methodology discussed in the Experiments section. Forclarity, the compound weight ratios were derived as a ratio of aparticular compound's percentage of the total peak area in oneexperiment to the same compound's percentage of the total peak area forthe 393/500/0 experiment (Experiment 13). When referring to experimentalconditions herein, the notational format “Temperature (° C.)/InitialArgon Pressure (psig)/Stress load (psi)” will be used as a shorthand torefer to the temperature, initial argon pressure and stress loading of aparticular experiment. For example, the notation “393/500/0” refers toan experiment conducted at 393° C., 500 psig initial argon pressure and0 psi stress load as present in Example 13. Thus the graphed i-C4 ton-C35 weight ratios do not include the weight contribution of theassociated gas phase product from any of the experiments. Further, thegraphed weight ratios do not include the weight contribution of anyliquid hydrocarbon compounds heavier than (i.e. having a longerretention time than) n-C35 or any unidentified (i.e., not listed in FIG.60) compounds from the WOGC data. The y-axis 600 represents the weightratio of a particular compound for a given experiment to the samecompound for the 393/500/0 experiment (Experiment 13). The x-axis 601contains the identity of each identified compound from i-C4 to n-C35.The data points occurring on line 602 represent the weight ratio of eachidentified i-C4 to n-C35 compound for the 393/500/400 experiment ofExample 15 to the 393/500/0 experiment of Experiment 13. The data pointsoccurring on line 603 represent the weight ratio of each identified i-C4to n-C35 compound for the 393/500/1000 experiment of Example 18 to the393/500/0 experiment of Experiment 13. The data points occurring on line604 represent the weight ratio of each identified i-C4 to n-C35 compoundfor the 393/200/400 experiment of Example 16 to the 393/500/0 experimentof Experiment 13. The data points occurring on line 605 represent theweight ratio of each identified i-C4 to n-C35 compound for the393/200/1000 experiment of Example 19 to the 393/500/0 experiment ofExperiment 13. The data points occurring on line 606 represent theweight ratio of each identified i-C4 to n-C35 compound for the 393/200/0experiment of Example 14 to the 393/500/0 experiment of Experiment 13.The data points occurring on line 607 represent the weight ratio of eachidentified i-C4 to n-C35 compound for the 393/50/400 experiment ofExample 17 to the 393/500/0 experiment of Experiment 13.

From FIG. 60 it can also be seen that the hydrocarbon liquids producedin the two 1,000 psi stressed experiments, represented by data points online 603 & 605, generally contain a decreased weight ratio of normalalkane hydrocarbon compounds for n-C8 and heavier normal alkanehydrocarbon compounds, including for example n-C9 through n-C35. It alsocan be seen that for the two 1,000 psi stress experiments, the lowerinitial argon pressure (200 psig argon) experiment represented by line605 is generally more depleted of normal hydrocarbon compounds relativeto the higher initial argon pressure (500 psig argon) experimentrepresented by line 603. From FIG. 60 it can also be seen that thehydrocarbon liquid produced in the three 400 psi stressed experiments,represented by data points on line 602, 604 & 607, generally contain adecreased amount of normal hydrocarbon compounds for n-C8 and heavierrelative to the unstressed experiments (i.e., line 606 & the “1” line onthe y-axis representing Experiments 13 & 14) but a less depleted weightratio of normal hydrocarbon compounds relative to the 1,000 psi stressedexperiments (Lines 603 & 605). It also can be seen that for the three400 psi stress experiments, the lowest initial argon pressure (50 psigargon) experiment represented by line 607 is generally more depleted ofnormal compounds for n-C8 and heavier relative to the middle initialargon pressures (200 psig argon) experiment represented by line 604 andthe highest initial argon pressures (500 psig argon) experimentrepresented by line 602, with the middle initial argon pressures (200psig argon) experiment represented by line 604 generally falling betweenthe highest and lowest initial argon pressure experiments. It is alsoapparent that for normal hydrocarbon compounds lighted than n-C8 (e.g.,n-05, n-C6 & n-C7), the above described trends go in the oppositedirection with increasing stress and decreasing pressure. Thuspyrolyzing oil shale under increasing levels of stress appears todeplete the produced hydrocarbon liquid in normal hydrocarbon compoundsfor n-C8 and heavier while decreasing pressure also appears to decreasenormal hydrocarbon compound for n-C8 and heavier production. Further,pyrolyzing oil shale under increasing levels of stress appears to enrichthe produced hydrocarbon liquid in normal hydrocarbon compounds for n-C7and lighter while decreasing pressure also appears to increase normalhydrocarbon compound for n-C7 and lighter production. Trends apparentfor aromatic hydrocarbon compounds (e.g., benzene & toluene) and cyclichydrocarbon compounds (e.g., methyl cyclohexane & methyl cyclopentane)will be discussed further with regard to the C4-C19 GC data describedherein.

FIG. 61 is a graph of the weight ratio of each WOGC identified compoundoccurring from i-C4 to n-C35 for each of the six 375° C. experimentstested and analyzed by WOGC in the laboratory experiments (Examples7-12) discussed herein compared to the weight ratio of each identifiedcompound occurring from i-C4 to n-C35 for Example 6 conducted at 375°C., 500 psig initial argon pressure and 0 psi stress. The data wasobtained in a similar manner as discussed above for FIG. 60. The y-axis610 represents the weight ratio of a particular compound for a givenexperiment to the same compound for the 375/500/0 experiment (Experiment6). The x-axis 611 contains the identity of each identified compoundfrom i-C4 to n-C35. The data points occurring on line 612 represent theweight ratio of each identified i-C4 to n-C35 compound for the375/500/400 experiment of Example 8 to the 375/500/0 experiment ofExperiment 6. The data points occurring on line 613 represent the weightratio of each identified i-C4 to n-C35 compound for the 375/500/1000experiment of Example 11 to the 375/500/0 experiment of Experiment 6.The data points occurring on line 614 represent the weight ratio of eachidentified i-C4 to n-C35 compound for the 375/200/400 experiment ofExample 9 to the 375/500/0 experiment of Experiment 6. The data pointsoccurring on line 615 represent the weight ratio of each identified i-C4to n-C35 compound for the 375/200/1000 experiment of Example 12 to the375/500/0 experiment of Experiment 6. The data points occurring on line616 represent the weight ratio of each identified i-C4 to n-C35 compoundfor the 375/200/0 experiment of Example 7 to the 375/500/0 experiment ofExperiment 6. The data points occurring on line 617 represent the weightratio of each identified i-C4 to n-C35 compound for the 375/50/400experiment of Example 10 to the 375/500/0 experiment of Experiment 6.While the trends for the 375° C. data are not as consistent as thetrends discussed above for the 393° C. data, the same generalrelationships as discussed above for the 393° C. data are apparent forthe 375° C. data. Further, it is apparent that the magnitude of thedeviations from the zero line are not as great as for the 393° C. data.Thus it is apparent that temperature also has a significant effect onthe above discussed compositional changes.

From the above-described data, it can be seen that heating and pyrolysisof oil shale under increasing levels of stress results in a condensablehydrocarbon fluid product that is lighter (i.e., greater proportion oflower carbon number compounds or components relative to higher carbonnumber compounds or components) and contains a lower concentration ofnormal alkane hydrocarbon compounds. Such a product may be suitable forrefining into gasoline and distillate products. Further, such a product,either before or after further fractionation, may have utility as a feedstock for certain chemical processes.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have one or more of a total C7 to total C20weight ratio greater than 0.8, a total C8 to total C20 weight ratiogreater than 1.7, a total C9 to total C20 weight ratio greater than 2.5,a total C10 to total C20 weight ratio greater than 2.8, a total C11 tototal C20 weight ratio greater than 2.3, a total C12 to total C20 weightratio greater than 2.3, a total C13 to total C20 weight ratio greaterthan 2.9, a total C14 to total C20 weight ratio greater than 2.2, atotal C15 to total C20 weight ratio greater than 2.2, and a total C16 tototal C20 weight ratio greater than 1.6. In alternative embodiments thecondensable hydrocarbon portion has one or more of a total C7 to totalC20 weight ratio greater than 2.5, a total C8 to total C20 weight ratiogreater than 3.0, a total C9 to total C20 weight ratio greater than 3.5,a total C10 to total C20 weight ratio greater than 3.5, a total C11 tototal C20 weight ratio greater than 3.0, and a total C12 to total C20weight ratio greater than 3.0. In alternative embodiments thecondensable hydrocarbon portion has one or more of a total C7 to totalC20 weight ratio greater than 3.5, a total C8 to total C20 weight ratiogreater than 4.3, a total C9 to total C20 weight ratio greater than 4.5,a total C10 to total C20 weight ratio greater than 4.2, a total C11 tototal C20 weight ratio greater than 3.7, and a total C12 to total C20weight ratio greater than 3.5. As used in this paragraph and in theclaims, the phrase “one or more” followed by a listing of differentcompound or component ratios with the last ratio introduced by theconjunction “and” is meant to include a condensable hydrocarbon portionthat has at least one of the listed ratios or that has two or more, orthree or more, or four or more, etc., or all of the listed ratios.Further, a particular condensable hydrocarbon portion may also haveadditional ratios of different compounds or components that are notincluded in a particular sentence or claim and still fall within thescope of such a sentence or claim. The embodiments described in thisparagraph may be combined with any of the other aspects of the inventiondiscussed herein.

In some embodiments the condensable hydrocarbon portion has a total C7to total C20 weight ratio greater than 0.8. Alternatively, thecondensable hydrocarbon portion may have a total C7 to total C20 weightratio greater than 1.0, greater than 1.5, greater than 2.0, greater than2.5, greater than 3.5 or greater than 3.7. In alternative embodiments,the condensable hydrocarbon portion may have a total C7 to total C20weight ratio less than 10.0, less than 7.0, less than 5.0 or less than4.0. In some embodiments the condensable hydrocarbon portion has a totalC8 to total C20 weight ratio greater than 1.7. Alternatively, thecondensable hydrocarbon portion may have a total C8 to total C20 weightratio greater than 2.0, greater than 2.5, greater than 3.0, greater than4.0, greater than 4.4, or greater than 4.6. In alternative embodiments,the condensable hydrocarbon portion may have a total C8 to total C20weight ratio less than 7.0 or less than 6.0. In some embodiments thecondensable hydrocarbon portion has a total C9 to total C20 weight ratiogreater than 2.5. Alternatively, the condensable hydrocarbon portion mayhave a total C9 to total C20 weight ratio greater than 3.0, greater than4.0, greater than 4.5, or greater than 4.7. In alternative embodiments,the condensable hydrocarbon portion may have a total C9 to total C20weight ratio less than 7.0 or less than 6.0. In some embodiments thecondensable hydrocarbon portion has a total C10 to total C20 weightratio greater than 2.8. Alternatively, the condensable hydrocarbonportion may have a total C10 to total C20 weight ratio greater than 3.0,greater than 3.5, greater than 4.0, or greater than 4.3. In alternativeembodiments, the condensable hydrocarbon portion may have a total C10 tototal C20 weight ratio less than 7.0 or less than 6.0. In someembodiments the condensable hydrocarbon portion has a total C11 to totalC20 weight ratio greater than 2.3. Alternatively, the condensablehydrocarbon portion may have a total C11 to total C20 weight ratiogreater than 2.5, greater than 3.5, greater than 3.7, greater than 4.0.In alternative embodiments, the condensable hydrocarbon portion may havea total C11 to total C20 weight ratio less than 7.0 or less than 6.0. Insome embodiments the condensable hydrocarbon portion has a total C12 tototal C20 weight ratio greater than 2.3. Alternatively, the condensablehydrocarbon portion may have a total C12 to total C20 weight ratiogreater than 2.5, greater than 3.0, greater than 3.5, or greater than3.7. In alternative embodiments, the condensable hydrocarbon portion mayhave a total C12 to total C20 weight ratio less than 7.0 or less than6.0. In some embodiments the condensable hydrocarbon portion has a totalC13 to total C20 weight ratio greater than 2.9. Alternatively, thecondensable hydrocarbon portion may have a total C13 to total C20 weightratio greater than 3.0, greater than 3.1, or greater than 3.2. Inalternative embodiments, the condensable hydrocarbon portion may have atotal C13 to total C20 weight ratio less than 6.0 or less than 5.0. Insome embodiments the condensable hydrocarbon portion has a total C14 tototal C20 weight ratio greater than 2.2. Alternatively, the condensablehydrocarbon portion may have a total C14 to total C20 weight ratiogreater than 2.5, greater than 2.6, or greater than 2.7. In alternativeembodiments, the condensable hydrocarbon portion may have a total C14 tototal C20 weight ratio less than 6.0 or less than 4.0. In someembodiments the condensable hydrocarbon portion has a total C15 to totalC20 weight ratio greater than 2.2. Alternatively, the condensablehydrocarbon portion may have a total C15 to total C20 weight ratiogreater than 2.3, greater than 2.4, or greater than 2.6. In alternativeembodiments, the condensable hydrocarbon portion may have a total C15 tototal C20 weight ratio less than 6.0 or less than 4.0. In someembodiments the condensable hydrocarbon portion has a total C16 to totalC20 weight ratio greater than 1.6. Alternatively, the condensablehydrocarbon portion may have a total C16 to total C20 weight ratiogreater than 1.8, greater than 2.3, or greater than 2.5. In alternativeembodiments, the condensable hydrocarbon portion may have a total C16 tototal C20 weight ratio less than 5.0 or less than 4.0. Certain featuresof the present invention are described in terms of a set of numericalupper limits (e.g. “less than”) and a set of numerical lower limits(e.g. “greater than”) in the preceding paragraph. It should beappreciated that ranges formed by any combination of these limits arewithin the scope of the invention unless otherwise indicated. Theembodiments described in this paragraph may be combined with any of theother aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion may have the oneor more of a total C7 to total C25 weight ratio greater than 2.0, atotal C8 to total C25 weight ratio greater than 4.5, a total C9 to totalC25 weight ratio greater than 6.5, a total C10 to total C25 weight ratiogreater than 7.5, a total C11 to total C25 weight ratio greater than6.5, a total C12 to total C25 weight ratio greater than 6.5, a total C13to total C25 weight ratio greater than 8.0, a total C14 to total C25weight ratio greater than 6.0, a total C15 to total C25 weight ratiogreater than 6.0, a total C16 to total C25 weight ratio greater than4.5, a total C17 to total C25 weight ratio greater than 4.8, and a totalC18 to total C25 weight ratio greater than 4.5. In alternativeembodiments the condensable hydrocarbon portion has one or more of atotal C7 to total C25 weight ratio greater than 7.0, a total C8 to totalC25 weight ratio greater than 10.0, a total C9 to total C25 weight ratiogreater than 10.0, a total C10 to total C25 weight ratio greater than10.0, a total C11 to total C25 weight ratio greater than 8.0, and atotal C12 to total C25 weight ratio greater than 8.0. In alternativeembodiments the condensable hydrocarbon portion has one or more of atotal C7 to total C25 weight ratio greater than 13.0, a total C8 tototal C25 weight ratio greater than 17.0, a total C9 to total C25 weightratio greater than 17.0, a total C10 to total C25 weight ratio greaterthan 15.0, a total C11 to total C25 weight ratio greater than 14.0, anda total C12 to total C25 weight ratio greater than 13.0. As used in thisparagraph and in the claims, the phrase “one or more” followed by alisting of different compound or component ratios with the last ratiointroduced by the conjunction “and” is meant to include a condensablehydrocarbon portion that has at least one of the listed ratios or thathas two or more, or three or more, or four or more, etc., or all of thelisted ratios. Further, a particular condensable hydrocarbon portion mayalso have additional ratios of different compounds or components thatare not included in a particular sentence or claim and still fall withinthe scope of such a sentence or claim. The embodiments described in thisparagraph may be combined with any of the other aspects of the inventiondiscussed herein.

In some embodiments the condensable hydrocarbon portion has a total C7to total C25 weight ratio greater than 2.0. Alternatively, thecondensable hydrocarbon portion may have a total C7 to total C25 weightratio greater than 3.0, greater than 5.0, greater than 10.0, greaterthan 13.0, or greater than 15.0. In alternative embodiments, thecondensable hydrocarbon portion may have a total C7 to total C25 weightratio less than 30.0 or less than 25.0. In some embodiments thecondensable hydrocarbon portion has a total C8 to total C25 weight ratiogreater than 4.5. Alternatively, the condensable hydrocarbon portion mayhave a total C8 to total C25 weight ratio greater than 5.0, greater than7.0, greater than 10.0, greater than 15.0, or greater than 17.0. Inalternative embodiments, the condensable hydrocarbon portion may have atotal C8 to total C25 weight ratio less than 35.0, or less than 30.0. Insome embodiments the condensable hydrocarbon portion has a total C9 tototal C25 weight ratio greater than 6.5. Alternatively, the condensablehydrocarbon portion may have a total C9 to total C25 weight ratiogreater than 8.0, greater than 10.0, greater than 15.0, greater than17.0, or greater than 19.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C9 to total C25 weight ratio lessthan 40.0 or less than 35.0. In some embodiments the condensablehydrocarbon portion has a total C10 to total C25 weight ratio greaterthan 7.5. Alternatively, the condensable hydrocarbon portion may have atotal C10 to total C25 weight ratio greater than 10.0, greater than14.0, or greater than 17.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C10 to total C25 weight ratio lessthan 35.0 or less than 30.0. In some embodiments the condensablehydrocarbon portion has a total C11 to total C25 weight ratio greaterthan 6.5. Alternatively, the condensable hydrocarbon portion may have atotal C11 to total C25 weight ratio greater than 8.5, greater than 10.0,greater than 12.0, or greater than 14.0. In alternative embodiments, thecondensable hydrocarbon portion may have a total C11 to total C25 weightratio less than 35.0 or less than 30.0. In some embodiments thecondensable hydrocarbon portion has a total C12 to total C25 weightratio greater than 6.5. Alternatively, the condensable hydrocarbonportion may have a total C12 to total C25 weight ratio greater than 8.5,a total C12 to total C25 weight ratio greater than 10.0, greater than12.0, or greater than 14.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C12 to total C25 weight ratio lessthan 30.0 or less than 25.0. In some embodiments the condensablehydrocarbon portion has a total C13 to total C25 weight ratio greaterthan 8.0. Alternatively, the condensable hydrocarbon portion may have atotal C13 to total C25 weight ratio greater than 10.0, greater than12.0, or greater than 14.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C13 to total C25 weight ratio lessthan 25.0 or less than 20.0. In some embodiments the condensablehydrocarbon portion has a total C14 to total C25 weight ratio greaterthan 6.0. Alternatively, the condensable hydrocarbon portion may have atotal C14 to total C25 weight ratio greater than 8.0, greater than 10.0,or greater than 12.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C14 to total C25 weight ratio lessthan 25.0 or less than 20.0. In some embodiments the condensablehydrocarbon portion has a total C15 to total C25 weight ratio greaterthan 6.0. Alternatively, the condensable hydrocarbon portion may have atotal C15 to total C25 weight ratio greater than 8.0, or greater than10.0. In alternative embodiments, the condensable hydrocarbon portionmay have a total C15 to total C25 weight ratio less than 25.0 or lessthan 20.0. In some embodiments the condensable hydrocarbon portion has atotal C16 to total C25 weight ratio greater than 4.5. Alternatively, thecondensable hydrocarbon portion may have a total C16 to total C25 weightratio greater than 6.0, greater than 8.0, or greater than 10.0. Inalternative embodiments, the condensable hydrocarbon portion may have atotal C16 to total C25 weight ratio less than 20.0 or less than 15.0. Insome embodiments the condensable hydrocarbon portion has a total C17 tototal C25 weight ratio greater than 4.8. Alternatively, the condensablehydrocarbon portion may have a total C17 to total C25 weight ratiogreater than 5.5 or greater than 7.0. In alternative embodiments, thecondensable hydrocarbon portion may have a total C17 to total C25 weightratio less than 20.0. In some embodiments the condensable hydrocarbonportion has a total C18 to total C25 weight ratio greater than 4.5.Alternatively, the condensable hydrocarbon portion may have a total C18to total C25 weight ratio greater than 5.0 or greater than 5.5. Inalternative embodiments, the condensable hydrocarbon portion may have atotal C18 to total C25 weight ratio less than 15.0. Certain features ofthe present invention are described in terms of a set of numerical upperlimits (e.g. “less than”) and a set of numerical lower limits (e.g.“greater than”) in the preceding paragraph. It should be appreciatedthat ranges formed by any combination of these limits are within thescope of the invention unless otherwise indicated. The embodimentsdescribed in this paragraph may be combined with any of the otheraspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion may have the oneor more of a total C7 to total C29 weight ratio greater than 3.5, atotal C8 to total C29 weight ratio greater than 9.0, a total C9 to totalC29 weight ratio greater than 12.0, a total C10 to total C29 weightratio greater than 15.0, a total C11 to total C29 weight ratio greaterthan 13.0, a total C12 to total C29 weight ratio greater than 12.5, anda total C13 to total C29 weight ratio greater than 16.0, a total C14 tototal C29 weight ratio greater than 12.0, a total C15 to total C29weight ratio greater than 12.0, a total C16 to total C29 weight ratiogreater than 9.0, a total C17 to total C29 weight ratio greater than10.0, a total C18 to total C29 weight ratio greater than 8.8, a totalC19 to total C29 weight ratio greater than 7.0, a total C20 to total C29weight ratio greater than 6.0, a total C21 to total C29 weight ratiogreater than 5.5, and a total C22 to total C29 weight ratio greater than4.2. In alternative embodiments the condensable hydrocarbon portion hasone or more of a total C7 to total C29 weight ratio greater than 16.0, atotal C8 to total C29 weight ratio greater than 19.0, a total C9 tototal C29 weight ratio greater than 20.0, a total C10 to total C29weight ratio greater than 18.0, a total C11 to total C29 weight ratiogreater than 16.0, a total C12 to total C29 weight ratio greater than15.0, and a total C13 to total C29 weight ratio greater than 17.0, atotal C14 to total C29 weight ratio greater than 13.0, a total C15 tototal C29 weight ratio greater than 13.0, a total C16 to total C29weight ratio greater than 10.0, a total C17 to total C29 weight ratiogreater than 11.0, a total C18 to total C29 weight ratio greater than9.0, a total C19 to total C29 weight ratio greater than 8.0, a total C20to total C29 weight ratio greater than 6.5, and a total C21 to total C29weight ratio greater than 6.0. In alternative embodiments thecondensable hydrocarbon portion has one or more of a total C7 to totalC29 weight ratio greater than 24.0, a total C8 to total C29 weight ratiogreater than 30.0, a total C9 to total C29 weight ratio greater than32.0, a total C10 to total C29 weight ratio greater than 30.0, a totalC11 to total C29 weight ratio greater than 27.0, a total C12 to totalC29 weight ratio greater than 25.0, and a total C13 to total C29 weightratio greater than 22.0, a total C14 to total C29 weight ratio greaterthan 18.0, a total C15 to total C29 weight ratio greater than 18.0, atotal C16 to total C29 weight ratio greater than 16.0, a total C17 tototal C29 weight ratio greater than 13.0, a total C18 to total C29weight ratio greater than 10.0, a total C19 to total C29 weight ratiogreater than 9.0, and a total C20 to total C29 weight ratio greater than7.0. As used in this paragraph and in the claims, the phrase “one ormore” followed by a listing of different compound or component ratioswith the last ratio introduced by the conjunction “and” is meant toinclude a condensable hydrocarbon portion that has at least one of thelisted ratios or that has two or more, or three or more, or four ormore, etc., or all of the listed ratios. Further, a particularcondensable hydrocarbon portion may also have additional ratios ofdifferent compounds or components that are not included in a particularsentence or claim and still fall within the scope of such a sentence orclaim. The embodiments described in this paragraph may be combined withany of the other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion has a total C7to total C29 weight ratio greater than 3.5. Alternatively, thecondensable hydrocarbon portion may have a total C7 to total C29 weightratio greater than 5.0, greater than 10.0, greater than 18.0, greaterthan 20.0, or greater than 24.0. In alternative embodiments, thecondensable hydrocarbon portion may have a total C7 to total C29 weightratio less than 60.0 or less than 50.0. In some embodiments thecondensable hydrocarbon portion has a total C8 to total C29 weight ratiogreater than 9.0. Alternatively, the condensable hydrocarbon portion mayhave a total C8 to total C29 weight ratio greater than 10.0, greaterthan 18.0, greater than 20.0, greater than 25.0, or greater than 30.0.In alternative embodiments, the condensable hydrocarbon portion may havea total C8 to total C29 weight ratio less than 85.0 or less than 75.0.In some embodiments the condensable hydrocarbon portion has a total C9to total C29 weight ratio greater than 12.0. Alternatively, thecondensable hydrocarbon portion may have a total C9 to total C29 weightratio greater than 15.0, greater than 20.0, greater than 23.0, greaterthan 27.0, or greater than 32.0. In alternative embodiments, thecondensable hydrocarbon portion may have a total C9 to total C29 weightratio less than 85.0 or less than 75.0. In some embodiments thecondensable hydrocarbon portion has a total C10 to total C29 weightratio greater than 15.0. Alternatively, the condensable hydrocarbonportion may have a total C10 to total C29 weight ratio greater than18.0, greater than 22.0, or greater than 28.0. In alternativeembodiments, the condensable hydrocarbon portion may have a total C10 tototal C29 weight ratio less than 80.0 or less than 70.0. In someembodiments the condensable hydrocarbon portion has a total C11 to totalC29 weight ratio greater than 13.0. Alternatively, the condensablehydrocarbon portion may have a total C11 to total C29 weight ratiogreater than 16.0, greater than 18.0, greater than 24.0, or greater than27.0. In alternative embodiments, the condensable hydrocarbon portionmay have a total C11 to total C29 weight ratio less than 75.0 or lessthan 65.0. In some embodiments the condensable hydrocarbon portion has atotal C12 to total C29 weight ratio greater than 12.5. Alternatively,the condensable hydrocarbon portion may have a total C12 to total C29weight ratio greater than 14.5, greater than 18.0, greater than 22.0, orgreater than 25.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C12 to total C29 weight ratio lessthan 75.0 or less than 65.0. In some embodiments the condensablehydrocarbon portion has a total C13 to total C29 weight ratio greaterthan 16.0. Alternatively, the condensable hydrocarbon portion may have atotal C13 to total C29 weight ratio greater than 18.0, greater than20.0, or greater than 22.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C13 to total C29 weight ratio lessthan 70.0 or less than 60.0. In some embodiments the condensablehydrocarbon portion has a total C14 to total C29 weight ratio greaterthan 12.0. Alternatively, the condensable hydrocarbon portion may have atotal C14 to total C29 weight ratio greater than 14.0, greater than16.0, or greater than 18.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C14 to total C29 weight ratio lessthan 60.0 or less than 50.0. In some embodiments the condensablehydrocarbon portion has a total C15 to total C29 weight ratio greaterthan 12.0. Alternatively, the condensable hydrocarbon portion may have atotal C15 to total C29 weight ratio greater than 15.0 or greater than18.0. In alternative embodiments, the condensable hydrocarbon portionmay have a total C15 to total C29 weight ratio less than 60.0 or lessthan 50.0. In some embodiments the condensable hydrocarbon portion has atotal C16 to total C29 weight ratio greater than 9.0. Alternatively, thecondensable hydrocarbon portion may have a total C16 to total C29 weightratio greater than 10.0, greater than 13.0, or greater than 16.0. Inalternative embodiments, the condensable hydrocarbon portion may have atotal C16 to total C29 weight ratio less than 55.0 or less than 45.0. Insome embodiments the condensable hydrocarbon portion has a total C17 tototal C29 weight ratio greater than 10.0. Alternatively, the condensablehydrocarbon portion may have a total C17 to total C29 weight ratiogreater than 11.0 or greater than 12.0. In alternative embodiments, thecondensable hydrocarbon portion may have a total C17 to total C29 weightratio less than 45.0. In some embodiments the condensable hydrocarbonportion has a total C18 to total C29 weight ratio greater than 8.8.Alternatively, the condensable hydrocarbon portion may have a total C18to total C29 weight ratio greater than 9.0 or greater than 10.0. Inalternative embodiments, the condensable hydrocarbon portion may have atotal C18 to total C29 weight ratio less than 35.0. In some embodimentsthe condensable hydrocarbon portion has a total C19 to total C29 weightratio greater than 7.0. Alternatively, the condensable hydrocarbonportion may have a total C19 to total C29 weight ratio greater than 8.0or greater than 9.0. In alternative embodiments, the condensablehydrocarbon portion may have a total C19 to total C29 weight ratio lessthan 30.0. Certain features of the present invention are described interms of a set of numerical upper limits (e.g. “less than”) and a set ofnumerical lower limits (e.g. “greater than”) in the preceding paragraph.It should be appreciated that ranges formed by any combination of theselimits are within the scope of the invention unless otherwise indicated.The embodiments described in this paragraph may be combined with any ofthe other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion may have the oneor more of a total C9 to total C20 weight ratio between 2.5 and 6.0, atotal C10 to total C20 weight ratio between 2.8 and 7.3, a total C11 tototal C20 weight ratio between 2.6 and 6.5, a total C12 to total C20weight ratio between 2.6 and 6.4 and a total C13 to total C20 weightratio between 3.2 and 8.0. In alternative embodiments the condensablehydrocarbon portion has one or more of a total C9 to total C20 weightratio between 3.0 and 5.5, a total C10 to total C20 weight ratio between3.2 and 7.0, a total C11 to total C20 weight ratio between 3.0 and 6.0,a total C12 to total C20 weight ratio between 3.0 and 6.0, and a totalC13 to total C20 weight ratio between 3.3 and 7.0. In alternativeembodiments the condensable hydrocarbon portion has one or more of atotal C9 to total C20 weight ratio between 4.6 and 5.5, a total C10 tototal C20 weight ratio between 4.2 and 7.0, a total C11 to total C20weight ratio between 3.7 and 6.0, a total C12 to total C20 weight ratiobetween 3.6 and 6.0, and a total C13 to total C20 weight ratio between3.4 and 7.0. As used in this paragraph and in the claims, the phrase“one or more” followed by a listing of different compound or componentratios with the last ratio introduced by the conjunction “and” is meantto include a condensable hydrocarbon portion that has at least one ofthe listed ratios or that has two or more, or three or more, or four ormore, etc., or all of the listed ratios. Further, a particularcondensable hydrocarbon portion may also have additional ratios ofdifferent compounds or components that are not included in a particularsentence or claim and still fall within the scope of such a sentence orclaim. The embodiments described in this paragraph may be combined withany of the other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion has a total C9to total C20 weight ratio between 2.5 and 6.0. Alternatively, thecondensable hydrocarbon portion may have a total C9 to total C20 weightratio between 3.0 and 5.8, between 3.5 and 5.8, between 4.0 and 5.8,between 4.5 and 5.8, between 4.6 and 5.8, or between 4.7 and 5.8. Insome embodiments the condensable hydrocarbon portion has a total C10 tototal C20 weight ratio between 2.8 and 7.3. Alternatively, thecondensable hydrocarbon portion may have a total C10 to total C20 weightratio between 3.0 and 7.2, between 3.5 and 7.0, between 4.0 and 7.0,between 4.2 and 7.0, between 4.3 and 7.0, or between 4.4 and 7.0. Insome embodiments the condensable hydrocarbon portion has a total C11 tototal C20 weight ratio between 2.6 and 6.5. Alternatively, thecondensable hydrocarbon portion may have a total C11 to total C20 weightratio between 2.8 and 6.3, between 3.5 and 6.3, between 3.7 and 6.3,between 3.8 and 6.3, between 3.9 and 6.2, or between 4.0 and 6.2. Insome embodiments the condensable hydrocarbon portion has a total C12 tototal C20 weight ratio between 2.6 and 6.4. Alternatively, thecondensable hydrocarbon portion may have a total C12 to total C20 weightratio between 2.8 and 6.2, between 3.2 and 6.2, between 3.5 and 6.2,between 3.6 and 6.2, between 3.7 and 6.0, or between 3.8 and 6.0. Insome embodiments the condensable hydrocarbon portion has a total C13 tototal C20 weight ratio between 3.2 and 8.0. Alternatively, thecondensable hydrocarbon portion may have a total C13 to total C20 weightratio between 3.3 and 7.8, between 3.3 and 7.0, between 3.4 and 7.0,between 3.5 and 6.5, or between 3.6 and 6.0. The embodiments describedin this paragraph may be combined with any of the other aspects of theinvention discussed herein.

In some embodiments the condensable hydrocarbon portion may have one ormore of a total C10 to total C25 weight ratio between 7.1 and 24.5, atotal C11 to total C25 weight ratio between 6.5 and 22.0, a total C12 tototal C25 weight ratio between 6.5 and 22.0, and a total C13 to totalC25 weight ratio between 8.0 and 27.0. In alternative embodiments thecondensable hydrocarbon portion has one or more of a total C10 to totalC25 weight ratio between 10.0 and 24.0, a total C11 to total C25 weightratio between 10.0 and 21.5, a total C12 to total C25 weight ratiobetween 10.0 and 21.5, and a total C13 to total C25 weight ratio between9.0 and 25.0. In alternative embodiments the condensable hydrocarbonportion has one or more of a total C10 to total C25 weight ratio between14.0 and 24.0, a total C11 to total C25 weight ratio between 12.5 and21.5, a total C12 to total C25 weight ratio between 12.0 and 21.5, and atotal C13 to total C25 weight ratio between 10.5 and 25.0. As used inthis paragraph and in the claims, the phrase “one or more” followed by alisting of different compound or component ratios with the last ratiointroduced by the conjunction “and” is meant to include a condensablehydrocarbon portion that has at least one of the listed ratios or thathas two or more, or three or more, or four or more, etc., or all of thelisted ratios. Further, a particular condensable hydrocarbon portion mayalso have additional ratios of different compounds or components thatare not included in a particular sentence or claim and still fall withinthe scope of such a sentence or claim. The embodiments described in thisparagraph may be combined with any of the other aspects of the inventiondiscussed herein.

In some embodiments the condensable hydrocarbon portion has a total C10to total C25 weight ratio between 7.1 and 24.5. Alternatively, thecondensable hydrocarbon portion may have a total C10 to total C25 weightratio between 7.5 and 24.5, between 12.0 and 24.5, between 13.8 and24.5, between 14.0 and 24.5, or between 15.0 and 24.5. In someembodiments the condensable hydrocarbon portion has a total C11 to totalC25 weight ratio between 6.5 and 22.0. Alternatively, the condensablehydrocarbon portion may have a total C11 to total C25 weight ratiobetween 7.0 and 21.5, between 10.0 and 21.5, between 12.5 and 21.5,between 13.0 and 21.5, between 13.7 and 21.5, or between 14.5 and 21.5.In some embodiments the condensable hydrocarbon portion has a total C12to total C25 weight ratio between 10.0 and 21.5. Alternatively, thecondensable hydrocarbon portion may have a total C12 to total C25 weightratio between 10.5 and 21.0, between 11.0 and 21.0, between 12.0 and21.0, between 12.5 and 21.0, between 13.0 and 21.0, or between 13.5 and21.0. In some embodiments the condensable hydrocarbon portion has atotal C13 to total C25 weight ratio between 8.0 and 27.0. Alternatively,the condensable hydrocarbon portion may have a total C13 to total C25weight ratio between 9.0 and 26.0, between 10.0 and 25.0, between 10.5and 25.0, between 11.0 and 25.0, or between 11.5 and 25.0. Theembodiments described in this paragraph may be combined with any of theother aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion may have one ormore of a total C10 to total C29 weight ratio between 15.0 and 60.0, atotal C11 to total C29 weight ratio between 13.0 and 54.0, a total C12to total C29 weight ratio between 12.5 and 53.0, and a total C13 tototal C29 weight ratio between 16.0 and 65.0. In alternative embodimentsthe condensable hydrocarbon portion has one or more of a total C10 tototal C29 weight ratio between 17.0 and 58.0, a total C11 to total C29weight ratio between 15.0 and 52.0, a total C12 to total C29 weightratio between 14.0 and 50.0, and a total C13 to total C29 weight ratiobetween 17.0 and 60.0. In alternative embodiments the condensablehydrocarbon portion has one or more of a total C10 to total C29 weightratio between 20.0 and 58.0, a total C11 to total C29 weight ratiobetween 18.0 and 52.0, a total C12 to total C29 weight ratio between18.0 and 50.0, and a total C13 to total C29 weight ratio between 18.0and 50.0. As used in this paragraph and in the claims, the phrase “oneor more” followed by a listing of different compound or component ratioswith the last ratio introduced by the conjunction “and” is meant toinclude a condensable hydrocarbon portion that has at least one of thelisted ratios or that has two or more, or three or more, or four ormore, etc., or all of the listed ratios. Further, a particularcondensable hydrocarbon portion may also have additional ratios ofdifferent compounds or components that are not included in a particularsentence or claim and still fall within the scope of such a sentence orclaim. The embodiments described in this paragraph may be combined withany of the other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion has a total C10to total C29 weight ratio between 15.0 and 60.0. Alternatively, thecondensable hydrocarbon portion may have a total C10 to total C29 weightratio between 18.0 and 58.0, between 20.0 and 58.0, between 24.0 and58.0, between 27.0 and 58.0, or between 30.0 and 58.0. In someembodiments the condensable hydrocarbon portion has a total C11 to totalC29 weight ratio between 13.0 and 54.0. Alternatively, the condensablehydrocarbon portion may have a total C11 to total C29 weight ratiobetween 15.0 and 53.0, between 18.0 and 53.0, between 20.0 and 53.0,between 22.0 and 53.0, between 25.0 and 53.0, or between 27.0 and 53.0.In some embodiments the condensable hydrocarbon portion has a total C12to total C29 weight ratio between 12.5 and 53.0. Alternatively, thecondensable hydrocarbon portion may have a total C12 to total C29 weightratio between 14.5 and 51.0, between 16.0 and 51.0, between 18.0 and51.0, between 20.0 and 51.0, between 23.0 and 51.0, or between 25.0 and51.0. In some embodiments the condensable hydrocarbon portion has atotal C13 to total C29 weight ratio between 16.0 and 65.0.Alternatively, the condensable hydrocarbon portion may have a total C13to total C29 weight ratio between 17.0 and 60.0, between 18.0 and 60.0,between 20.0 and 60.0, between 22.0 and 60.0, or between 25.0 and 60.0.The embodiments described in this paragraph may be combined with any ofthe other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion may have one ormore of a normal-C7 to normal-C20 weight ratio greater than 0.9, anormal-C8 to normal-C20 weight ratio greater than 2.0, a normal-C9 tonormal-C20 weight ratio greater than 1.9, a normal-C10 to normal-C20weight ratio greater than 2.2, a normal-C11 to normal-C20 weight ratiogreater than 1.9, a normal-C12 to normal-C20 weight ratio greater than1.9, a normal-C13 to normal-C20 weight ratio greater than 2.3, anormal-C14 to normal-C20 weight ratio greater than 1.8, a normal-C15 tonormal-C20 weight ratio greater than 1.8, and normal-C16 to normal-C20weight ratio greater than 1.3. In alternative embodiments thecondensable hydrocarbon portion has one or more of a normal-C7 tonormal-C20 weight ratio greater than 4.4, a normal-C8 to normal-C20weight ratio greater than 3.7, a normal-C9 to normal-C20 weight ratiogreater than 3.5, a normal-C10 to normal-C20 weight ratio greater than3.4, a normal-C11 to normal-C20 weight ratio greater than 3.0, and anormal-C12 to normal-C20 weight ratio greater than 2.7. In alternativeembodiments the condensable hydrocarbon portion has one or more of anormal-C7 to normal-C20 weight ratio greater than 4.9, a normal-C8 tonormal-C20 weight ratio greater than 4.5, a normal-C9 to normal-C20weight ratio greater than 4.4, a normal-C10 to normal-C20 weight ratiogreater than 4.1, a normal-C11 to normal-C20 weight ratio greater than3.7, and a normal-C12 to normal-C20 weight ratio greater than 3.0. Asused in this paragraph and in the claims, the phrase “one or more”followed by a listing of different compound or component ratios with thelast ratio introduced by the conjunction “and” is meant to include acondensable hydrocarbon portion that has at least one of the listedratios or that has two or more, or three or more, or four or more, etc.,or all of the listed ratios. Further, a particular condensablehydrocarbon portion may also have additional ratios of differentcompounds or components that are not included in a particular sentenceor claim and still fall within the scope of such a sentence or claim.The embodiments described in this paragraph may be combined with any ofthe other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion has a normal-C7to normal-C20 weight ratio greater than 0.9. Alternatively, thecondensable hydrocarbon portion may have a normal-C7 to normal-C20weight ratio greater than 1.0, than 2.0, greater than 3.0, greater than4.0, greater than 4.5, or greater than 5.0. In alternative embodiments,the condensable hydrocarbon portion may have a normal-C7 to normal-C20weight ratio less than 8.0 or less than 7.0. In some embodiments thecondensable hydrocarbon portion has a normal-C8 to normal-C20 weightratio greater than 1.7. Alternatively, the condensable hydrocarbonportion may have a normal-C8 to normal-C20 weight ratio greater than2.0, greater than 2.5, greater than 3.0, greater than 3.5, greater than4.0, or greater than 4.4. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C8 to normal-C20 weight ratio lessthan 8.0 or less than 7.0. In some embodiments the condensablehydrocarbon portion has a normal-C9 to normal-C20 weight ratio greaterthan 1.9. Alternatively, the condensable hydrocarbon portion may have anormal-C9 to normal-C20 weight ratio greater than 2.0, greater than 3.0,greater than 4.0, or greater than 4.5. In alternative embodiments, thecondensable hydrocarbon portion may have a normal-C9 to normal-C20weight ratio less than 7.0 or less than 6.0. In some embodiments thecondensable hydrocarbon portion has a normal-C10 to normal-C20 weightratio greater than 2.2. Alternatively, the condensable hydrocarbonportion may have a normal-C10 to normal-C20 weight ratio greater than2.8, greater than 3.3, greater than 3.5, or greater than 4.0. Inalternative embodiments, the condensable hydrocarbon portion may have anormal-C10 to normal-C20 weight ratio less than 7.0 or less than 6.0. Insome embodiments the condensable hydrocarbon portion has a normal-C11 tonormal-C20 weight ratio greater than 1.9. Alternatively, the condensablehydrocarbon portion may have a normal-C11 to normal-C20 weight ratiogreater than 2.5, greater than 3.0, greater than 3.5, or greater than3.7. In alternative embodiments, the condensable hydrocarbon portion mayhave a normal-C11 to normal-C20 weight ratio less than 7.0 or less than6.0. In some embodiments the condensable hydrocarbon portion has anormal-C12 to normal-C20 weight ratio greater than 1.9. Alternatively,the condensable hydrocarbon portion may have a normal-C12 to normal-C20weight ratio greater than 2.0, greater than 2.2, greater than 2.6, orgreater than 3.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C12 to normal-C20 weight ratioless than 7.0 or less than 6.0. In some embodiments the condensablehydrocarbon portion has a normal-C13 to normal-C20 weight ratio greaterthan 2.3. Alternatively, the condensable hydrocarbon portion may have anormal-C13 to normal-C20 weight ratio greater than 2.5, greater than2.7, or greater than 3.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C13 to normal-C20 weight ratioless than 6.0 or less than 5.0. In some embodiments the condensablehydrocarbon portion has a normal-C14 to normal-C20 weight ratio greaterthan 1.8. Alternatively, the condensable hydrocarbon portion may have anormal-C14 to normal-C20 weight ratio greater than 2.0, greater than2.2, or greater than 2.5. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C14 to normal-C20 weight ratioless than 6.0 or less than 4.0. In some embodiments the condensablehydrocarbon portion has a normal-C15 to normal-C20 weight ratio greaterthan 1.8. Alternatively, the condensable hydrocarbon portion may have anormal-C15 to normal-C20 weight ratio greater than 2.0, greater than2.2, or greater than 2.4. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C15 to normal-C20 weight ratioless than 6.0 or less than 4.0. In some embodiments the condensablehydrocarbon portion has a normal-C16 to normal-C20 weight ratio greaterthan 1.3. Alternatively, the condensable hydrocarbon portion may have anormal-C16 to normal-C20 weight ratio greater than 1.5, greater than1.7, or greater than 2.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C16 to normal-C20 weight ratioless than 5.0 or less than 4.0. Certain features of the presentinvention are described in terms of a set of numerical upper limits(e.g. “less than”) and a set of numerical lower limits (e.g. “greaterthan”) in the preceding paragraph. It should be appreciated that rangesformed by any combination of these limits are within the scope of theinvention unless otherwise indicated. The embodiments described in thisparagraph may be combined with any of the other aspects of the inventiondiscussed herein.

In some embodiments the condensable hydrocarbon portion may have one ormore of a normal-C7 to normal-C25 weight ratio greater than 1.9, anormal-C8 to normal-C25 weight ratio greater than 3.9, a normal-C9 tonormal-C25 weight ratio greater than 3.7, a normal-C10 to normal-C25weight ratio greater than 4.4, a normal-C11 to normal-C25 weight ratiogreater than 3.8, a normal-C12 to normal-C25 weight ratio greater than3.7, a normal-C13 to normal-C25 weight ratio greater than 4.7, anormal-C14 to normal-C25 weight ratio greater than 3.7, a normal-C15 tonormal-C25 weight ratio greater than 3.7, a normal-C16 to normal-C25weight ratio greater than 2.5, a normal-C17 to normal-C25 weight ratiogreater than 3.0, and a normal-C18 to normal-C25 weight ratio greaterthan 3.4. In alternative embodiments the condensable hydrocarbon portionhas one or more of a normal-C7 to normal-C25 weight ratio greater than10, a normal-C8 to normal-C25 weight ratio greater than 8.0, a normal-C9to normal-C25 weight ratio greater than 7.0, a normal-C10 to normal-C25weight ratio greater than 7.0, a normal-C11 to normal-C25 weight ratiogreater than 7.0, and a normal-C12 to normal-C25 weight ratio greaterthan 6.0. In alternative embodiments the condensable hydrocarbon portionhas one or more of a normal-C7 to normal-C25 weight ratio greater than10.0, a normal-C8 to normal-C25 weight ratio greater than 12.0, anormal-C9 to normal-C25 weight ratio greater than 11.0, a normal-C10 tonormal-C25 weight ratio greater than 11.0, a normal-C11 to normal-C25weight ratio greater than 9.0, and a normal-C12 to normal-C25 weightratio greater than 8.0. As used in this paragraph and in the claims, thephrase “one or more” followed by a listing of different compound orcomponent ratios with the last ratio introduced by the conjunction “and”is meant to include a condensable hydrocarbon portion that has at leastone of the listed ratios or that has two or more, or three or more, orfour or more, etc., or all of the listed ratios. Further, a particularcondensable hydrocarbon portion may also have additional ratios ofdifferent compounds or components that are not included in a particularsentence or claim and still fall within the scope of such a sentence orclaim. The embodiments described in this paragraph may be combined withany of the other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion has a normal-C7to normal-C25 weight ratio greater than 1.9. Alternatively, thecondensable hydrocarbon portion may have a normal-C7 to normal-C25weight ratio greater than 3.0, greater than 5.0, greater than 8.0,greater than 10.0, or greater than 13.0. In alternative embodiments, thecondensable hydrocarbon portion may have a normal-C7 to normal-C25weight ratio less than 35.0 or less than 25.0. In some embodiments thecondensable hydrocarbon portion has a normal-C8 to normal-C25 weightratio greater than 3.9. Alternatively, the condensable hydrocarbonportion may have a normal-C8 to normal-C25 weight ratio greater than4.5, greater than 6.0, greater than 8.0, greater than 10.0, or greaterthan 13.0. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C8 to normal-C25 weight ratio less than 35.0or less than 25.0. In some embodiments the condensable hydrocarbonportion has a normal-C9 to normal-C25 weight ratio greater than 3.7.Alternatively, the condensable hydrocarbon portion may have a normal-C9to normal-C25 weight ratio greater than 4.5, greater than 7.0, greaterthan 10.0, greater than 12.0, or greater than 13.0. In alternativeembodiments, the condensable hydrocarbon portion may have a normal-C9 tonormal-C25 weight ratio less than 35.0 or less than 25.0. In someembodiments the condensable hydrocarbon portion has a normal-C10 tonormal-C25 weight ratio greater than 4.4. Alternatively, the condensablehydrocarbon portion may have a normal-C10 to normal-C25 weight ratiogreater than 6.0, greater than 8.0, or greater than 11.0. In alternativeembodiments, the condensable hydrocarbon portion may have a normal-C10to normal-C25 weight ratio less than 35.0 or less than 25.0. In someembodiments the condensable hydrocarbon portion has a normal-C11 tonormal-C25 weight ratio greater than 3.8. Alternatively, the condensablehydrocarbon portion may have a normal-C11 to normal-C25 weight ratiogreater than 4.5, greater than 7.0, greater than 8.0, or greater than10.0. In alternative embodiments, the condensable hydrocarbon portionmay have a normal-C11 to normal-C25 weight ratio less than 35.0 or lessthan 25.0. In some embodiments the condensable hydrocarbon portion has anormal-C12 to normal-C25 weight ratio greater than 3.7. Alternatively,the condensable hydrocarbon portion may have a normal-C12 to normal-C25weight ratio greater than 4.5, greater than 6.0, greater than 7.0, orgreater than 8.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C12 to normal-C25 weight ratioless than 30.0 or less than 20.0. In some embodiments the condensablehydrocarbon portion has a normal-C13 to normal-C25 weight ratio greaterthan 4.7. Alternatively, the condensable hydrocarbon portion may have anormal-C13 to normal-C25 weight ratio greater than 5.0, greater than6.0, or greater than 7.5. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C13 to normal-C25 weight ratioless than 25.0 or less than 20.0. In some embodiments the condensablehydrocarbon portion has a normal-C14 to normal-C25 weight ratio greaterthan 3.7. Alternatively, the condensable hydrocarbon portion may have anormal-C14 to normal-C25 weight ratio greater than 4.5, greater than5.5, or greater than 7.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C14 to normal-C25 weight ratioless than 25.0 or less than 20.0. In some embodiments the condensablehydrocarbon portion has a normal-C15 to normal-C25 weight ratio greaterthan 3.7. Alternatively, the condensable hydrocarbon portion may have anormal-C15 to normal-C25 weight ratio greater than 4.2 or greater than5.0. In alternative embodiments, the condensable hydrocarbon portion mayhave a normal-C15 to normal-C25 weight ratio less than 25.0 or less than20.0. In some embodiments the condensable hydrocarbon portion has anormal-C16 to normal-C25 weight ratio greater than 2.5. Alternatively,the condensable hydrocarbon portion may have a normal-C16 to normal-C25weight ratio greater than 3.0, greater than 4.0, or greater than 5.0. Inalternative embodiments, the condensable hydrocarbon portion may have anormal-C16 to normal-C25 weight ratio less than 20.0 or less than 15.0.In some embodiments the condensable hydrocarbon portion has a normal-C17to normal-C25 weight ratio greater than 3.0. Alternatively, thecondensable hydrocarbon portion may have a normal-C17 to normal-C25weight ratio greater than 3.5 or greater than 4.0. In alternativeembodiments, the condensable hydrocarbon portion may have a normal-C17to normal-C25 weight ratio less than 20.0. In some embodiments thecondensable hydrocarbon portion has a normal-C18 to normal-C25 weightratio greater than 3.4. Alternatively, the condensable hydrocarbonportion may have a normal-C18 to normal-C25 weight ratio greater than3.6 or greater than 4.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C18 to normal-C25 weight ratioless than 15.0. Certain features of the present invention are describedin terms of a set of numerical upper limits (e.g. “less than”) and a setof numerical lower limits (e.g. “greater than”) in the precedingparagraph. It should be appreciated that ranges formed by anycombination of these limits are within the scope of the invention unlessotherwise indicated. The embodiments described in this paragraph may becombined with any of the other aspects of the invention discussedherein.

In some embodiments the condensable hydrocarbon portion may have one ormore of a normal-C7 to normal-C29 weight ratio greater than 18.0, anormal-C8 to normal-C29 weight ratio greater than 16.0, a normal-C9 tonormal-C29 weight ratio greater than 14.0, a normal-C10 to normal-C29weight ratio greater than 14.0, a normal-C11 to normal-C29 weight ratiogreater than 13.0, a normal-C12 to normal-C29 weight ratio greater than11.0, a normal-C13 to normal-C29 weight ratio greater than 10.0, anormal-C14 to normal-C29 weight ratio greater than 9.0, a normal-C15 tonormal-C29 weight ratio greater than 8.0, a normal-C16 to normal-C29weight ratio greater than 8.0, a normal-C17 to normal-C29 weight ratiogreater than 6.0, a normal-C18 to normal-C29 weight ratio greater than6.0, a normal-C19 to normal-C29 weight ratio greater than 5.0, anormal-C20 to normal-C29 weight ratio greater than 4.0, a normal-C21 tonormal-C29 weight ratio greater than 3.6, and a normal-C22 to normal-C29weight ratio greater than 2.8. In alternative embodiments thecondensable hydrocarbon portion has one or more of a normal-C7 tonormal-C29 weight ratio greater than 20.0, a normal-C8 to normal-C29weight ratio greater than 18.0, a normal-C9 to normal-C29 weight ratiogreater than 17.0, a normal-C10 to normal-C29 weight ratio greater than16.0, a normal-C11 to normal-C29 weight ratio greater than 15.0, anormal-C12 to normal-C29 weight ratio greater than 12.5, a normal-C13 tonormal-C29 weight ratio greater than 11.0, a normal-C14 to normal-C29weight ratio greater than 10.0, a normal-C15 to normal-C29 weight ratiogreater than 8.0, a normal-C16 to normal-C29 weight ratio greater than8.0, a normal-C17 to normal-C29 weight ratio greater than 7.0, anormal-C18 to normal-C29 weight ratio greater than 6.5, a normal-C19 tonormal-C29 weight ratio greater than 5.5, a normal-C20 to normal-C29weight ratio greater than 4.5, and a normal-C21 to normal-C29 weightratio greater than 4.0. In alternative embodiments the condensablehydrocarbon portion has one or more of a normal-C7 to normal-C29 weightratio greater than 23.0, a normal-C8 to normal-C29 weight ratio greaterthan 21.0, a normal-C9 to normal-C29 weight ratio greater than 20.0, anormal-C10 to normal-C29 weight ratio greater than 19.0, a normal-C11 tonormal-C29 weight ratio greater than 17.0, a normal-C12 to normal-C29weight ratio greater than 14.0, a normal-C13 to normal-C29 weight ratiogreater than 12.0, a normal-C14 to normal-C29 weight ratio greater than11.0, a normal-C15 to normal-C29 weight ratio greater than 9.0, anormal-C16 to normal-C29 weight ratio greater than 9.0, a normal-C17 tonormal-C29 weight ratio greater than 7.5, a normal-C18 to normal-C29weight ratio greater than 7.0, a normal-C19 to normal-C29 weight ratiogreater than 6.5, a normal-C20 to normal-C29 weight ratio greater than4.8, and a normal-C21 to normal-C29 weight ratio greater than 4.5. Asused in this paragraph and in the claims, the phrase “one or more”followed by a listing of different compound or component ratios with thelast ratio introduced by the conjunction “and” is meant to include acondensable hydrocarbon portion that has at least one of the listedratios or that has two or more, or three or more, or four or more, etc.,or all of the listed ratios. Further, a particular condensablehydrocarbon portion may also have additional ratios of differentcompounds or components that are not included in a particular sentenceor claim and still fall within the scope of such a sentence or claim.The embodiments described in this paragraph may be combined with any ofthe other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion has a normal-C7to normal-C29 weight ratio greater than 18.0. Alternatively, thecondensable hydrocarbon portion may have a normal-C7 to normal-C29weight ratio greater than 20.0, greater than 22.0, greater than 25.0,greater than 30.0, or greater than 35.0. In alternative embodiments, thecondensable hydrocarbon portion may have a normal-C7 to normal-C29weight ratio less than 70.0 or less than 60.0. In some embodiments thecondensable hydrocarbon portion has a normal-C8 to normal-C29 weightratio greater than 16.0. Alternatively, the condensable hydrocarbonportion may have a normal-C8 to normal-C29 weight ratio greater than18.0, greater than 22.0, greater than 25.0, greater than 27.0, orgreater than 30.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C8 to normal-C29 weight ratio lessthan 85.0 or less than 75.0. In some embodiments the condensablehydrocarbon portion has a normal-C9 to normal-C29 weight ratio greaterthan 14.0. Alternatively, the condensable hydrocarbon portion may have anormal-C9 to normal-C29 weight ratio greater than 18.0, greater than20.0, greater than 23.0, greater than 27.0, or greater than 30.0. Inalternative embodiments, the condensable hydrocarbon portion may have anormal-C9 to normal-C29 weight ratio less than 85.0 or less than 75.0.In some embodiments the condensable hydrocarbon portion has a normal-C10to normal-C29 weight ratio greater than 14.0. Alternatively, thecondensable hydrocarbon portion may have a normal-C10 to normal-C29weight ratio greater than 20.0, greater than 25.0, or greater than 30.0.In alternative embodiments, the condensable hydrocarbon portion may havea normal-C10 to normal-C29 weight ratio less than 80.0 or less than70.0. In some embodiments the condensable hydrocarbon portion has anormal-C11 to normal-C29 weight ratio greater than 13.0. Alternatively,the condensable hydrocarbon portion may have a normal-C11 to normal-C29weight ratio greater than 16.0, greater than 18.0, greater than 24.0, orgreater than 27.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C11 to normal-C29 weight ratioless than 75.0 or less than 65.0. In some embodiments the condensablehydrocarbon portion has a normal-C12 to normal-C29 weight ratio greaterthan 11.0. Alternatively, the condensable hydrocarbon portion may have anormal-C12 to normal-C29 weight ratio greater than 14.5, greater than18.0, greater than 22.0, or greater than 25.0. In alternativeembodiments, the condensable hydrocarbon portion may have a normal-C12to normal-C29 weight ratio less than 75.0 or less than 65.0. In someembodiments the condensable hydrocarbon portion has a normal-C13 tonormal-C29 weight ratio greater than 10.0. Alternatively, thecondensable hydrocarbon portion may have a normal-C13 to normal-C29weight ratio greater than 18.0, greater than 20.0, or greater than 22.0.In alternative embodiments, the condensable hydrocarbon portion may havea normal-C13 to normal-C29 weight ratio less than 70.0 or less than60.0. In some embodiments the condensable hydrocarbon portion has anormal-C14 to normal-C29 weight ratio greater than 9.0. Alternatively,the condensable hydrocarbon portion may have a normal-C14 to normal-C29weight ratio greater than 14.0, greater than 16.0, or greater than 18.0.In alternative embodiments, the condensable hydrocarbon portion may havea normal-C14 to normal-C29 weight ratio less than 60.0 or less than50.0. In some embodiments the condensable hydrocarbon portion has anormal-C15 to normal-C29 weight ratio greater than 8.0. Alternatively,the condensable hydrocarbon portion may have a normal-C15 to normal-C29weight ratio greater than 12.0 or greater than 16.0. In alternativeembodiments, the condensable hydrocarbon portion may have a normal-C15to normal-C29 weight ratio less than 60.0 or less than 50.0. In someembodiments the condensable hydrocarbon portion has a normal-C16 tonormal-C29 weight ratio greater than 8.0. Alternatively, the condensablehydrocarbon portion may have a normal-C16 to normal-C29 weight ratiogreater than 10.0, greater than 13.0, or greater than 15.0. Inalternative embodiments, the condensable hydrocarbon portion may have anormal-C16 to normal-C29 weight ratio less than 55.0 or less than 45.0.In some embodiments the condensable hydrocarbon portion has a normal-C17to normal-C29 weight ratio greater than 6.0. Alternatively, thecondensable hydrocarbon portion may have a normal-C17 to normal-C29weight ratio greater than 8.0 or greater than 12.0. In alternativeembodiments, the condensable hydrocarbon portion may have a normal-C17to normal-C29 weight ratio less than 45.0. In some embodiments thecondensable hydrocarbon portion has a normal-C18 to normal-C29 weightratio greater than 6.0. Alternatively, the condensable hydrocarbonportion may have a normal-C18 to normal-C29 weight ratio greater than8.0 or greater than 10.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C18 to normal-C29 weight ratioless than 35.0. In some embodiments the condensable hydrocarbon portionhas a normal-C19 to normal-C29 weight ratio greater than 5.0.Alternatively, the condensable hydrocarbon portion may have a normal-C19to normal-C29 weight ratio greater than 7.0 or greater than 9.0. Inalternative embodiments, the condensable hydrocarbon portion may have anormal-C19 to normal-C29 weight ratio less than 30.0. In someembodiments the condensable hydrocarbon portion has a normal-C20 tonormal-C29 weight ratio greater than 4.0. Alternatively, the condensablehydrocarbon portion may have a normal-C20 to normal-C29 weight ratiogreater than 6.0 or greater than 8.0. In alternative embodiments, thecondensable hydrocarbon portion may have a normal-C20 to normal-C29weight ratio less than 30.0. In some embodiments the condensablehydrocarbon portion has a normal-C21 to normal-C29 weight ratio greaterthan 3.6. Alternatively, the condensable hydrocarbon portion may have anormal-C21 to normal-C29 weight ratio greater than 4.0 or greater than6.0. In alternative embodiments, the condensable hydrocarbon portion mayhave a normal-C21 to normal-C29 weight ratio less than 30.0. In someembodiments the condensable hydrocarbon portion has a normal-C22 tonormal-C29 weight ratio greater than 2.8. Alternatively, the condensablehydrocarbon portion may have a normal-C22 to normal-C29 weight ratiogreater than 3.0. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C22 to normal-C29 weight ratioless than 30.0. Certain features of the present invention are describedin terms of a set of numerical upper limits (e.g. “less than”) and a setof numerical lower limits (e.g. “greater than”) in the precedingparagraph. It should be appreciated that ranges formed by anycombination of these limits are within the scope of the invention unlessotherwise indicated. The embodiments described in this paragraph may becombined with any of the other aspects of the invention discussedherein.

In some embodiments the condensable hydrocarbon portion may have one ormore of a normal-C10 to total C10 weight ratio less than 0.31, anormal-CuI to total C11 weight ratio less than 0.32, a normal-C12 tototal C12 weight ratio less than 0.29, a normal-C13 to total C13 weightratio less than 0.28, a normal-C14 to total C14 weight ratio less than0.31, a normal-C15 to total C15 weight ratio less than 0.27, anormal-C16 to total C16 weight ratio less than 0.31, a normal-C17 tototal C17 weight ratio less than 0.31, a normal-C18 to total C18 weightratio less than 0.37, normal-C19 to total C19 weight ratio less than0.37, a normal-C20 to total C20 weight ratio less than 0.37, anormal-C21 to total C21 weight ratio less than 0.37, a normal-C22 tototal C22 weight ratio less than 0.38, normal-C23 to total C23 weightratio less than 0.43, a normal-C24 to total C24 weight ratio less than0.48, and a normal-C25 to total C25 weight ratio less than 0.53. Inalternative embodiments the condensable hydrocarbon portion has one ormore of a normal-C11 to total C11 weight ratio less than 0.30, anormal-C12 to total C12 weight ratio less than 0.27, a normal-C13 tototal C13 weight ratio less than 0.26, a normal-C14 to total C14 weightratio less than 0.29, a normal-C15 to total C15 weight ratio less than0.24, a normal-C16 to total C16 weight ratio less than 0.25, anormal-C17 to total C17 weight ratio less than 0.29, a normal-C18 tototal C18 weight ratio less than 0.31, normal-C19 to total C19 weightratio less than 0.35, a normal-C20 to total C20 weight ratio less than0.33, a normal-C21 to total C21 weight ratio less than 0.33, anormal-C22 to total C22 weight ratio less than 0.35, normal-C23 to totalC23 weight ratio less than 0.40, a normal-C24 to total C24 weight ratioless than 0.45, and a normal-C25 to total C25 weight ratio less than0.49. In alternative embodiments the condensable hydrocarbon portion hasone or more of a normal-C11 to total C11 weight ratio less than 0.28, anormal-C12 to total C12 weight ratio less than 0.25, a normal-C13 tototal C13 weight ratio less than 0.24, a normal-C14 to total C14 weightratio less than 0.27, a normal-C15 to total C15 weight ratio less than0.22, a normal-C16 to total C16 weight ratio less than 0.23, anormal-C17 to total C17 weight ratio less than 0.25, a normal-C18 tototal C18 weight ratio less than 0.28, normal-C19 to total C19 weightratio less than 0.31, a normal-C20 to total C20 weight ratio less than0.29, a normal-C21 to total C21 weight ratio less than 0.30, anormal-C22 to total C22 weight ratio less than 0.28, normal-C23 to totalC23 weight ratio less than 0.33, a normal-C24 to total C24 weight ratioless than 0.40, and a normal-C25 to total C25 weight ratio less than0.45. As used in this paragraph and in the claims, the phrase “one ormore” followed by a listing of different compound or component ratioswith the last ratio introduced by the conjunction “and” is meant toinclude a condensable hydrocarbon portion that has at least one of thelisted ratios or that has two or more, or three or more, or four ormore, etc., or all of the listed ratios. Further, a particularcondensable hydrocarbon portion may also have additional ratios ofdifferent compounds or components that are not included in a particularsentence or claim and still fall within the scope of such a sentence orclaim. The embodiments described in this paragraph may be combined withany of the other aspects of the invention discussed herein.

In some embodiments the condensable hydrocarbon portion has a normal-C10to total C10 weight ratio less than 0.31. Alternatively, the condensablehydrocarbon portion may have a normal-C10 to total C10 weight ratio lessthan 0.30 or less than 0.29. In alternative embodiments, the condensablehydrocarbon portion may have a normal-C10 to total C10 weight ratiogreater than 0.15 or greater than 0.20. In some embodiments thecondensable hydrocarbon portion has a normal-C11 to total C11 weightratio less than 0.32. Alternatively, the condensable hydrocarbon portionmay have a normal-C11 to total C11 weight ratio less than 0.31, lessthan 0.30, or less than 0.29. In alternative embodiments, thecondensable hydrocarbon portion may have a normal-C11 to total C11weight ratio greater than 0.15 or greater than 0.20. In some embodimentsthe condensable hydrocarbon portion has a normal-C12 to total C12 weightratio less than 0.29. Alternatively, the condensable hydrocarbon portionmay have a normal-C12 to total C12 weight ratio less than 0.26, or lessthan 0.24. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C12 to total C12 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C13 to total C13 weight ratio less than0.28. Alternatively, the condensable hydrocarbon portion may have anormal-C13 to total C13 weight ratio less than 0.27, less than 0.25, orless than 0.23. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C13 to total C13 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C14 to total C14 weight ratio less than0.31. Alternatively, the condensable hydrocarbon portion may have anormal-C14 to total C14 weight ratio less than 0.30, less than 0.28, orless than 0.26. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C14 to total C14 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C15 to total C15 weight ratio less than0.27. Alternatively, the condensable hydrocarbon portion may have anormal-C15 to total C15 weight ratio less than 0.26, less than 0.24, orless than 0.22. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C15 to total C15 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C16 to total C16 weight ratio less than0.31. Alternatively, the condensable hydrocarbon portion may have anormal-C16 to total C16 weight ratio less than 0.29, less than 0.26, orless than 0.24. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C16 to total C16 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C17 to total C17 weight ratio less than0.31. Alternatively, the condensable hydrocarbon portion may have anormal-C17 to total C17 weight ratio less than 0.29, less than 0.27, orless than 0.25. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C17 to total C17 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C18 to total C18 weight ratio less than0.37. Alternatively, the condensable hydrocarbon portion may have anormal-C18 to total C18 weight ratio less than 0.35, less than 0.31, orless than 0.28. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C18 to total C18 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C19 to total C19 weight ratio less than0.37. Alternatively, the condensable hydrocarbon portion may have anormal-C19 to total C19 weight ratio less than 0.36, less than 0.34, orless than 0.31. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C19 to total C19 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C20 to total C20 weight ratio less than0.37. Alternatively, the condensable hydrocarbon portion may have anormal-C20 to total C20 weight ratio less than 0.35, less than 0.32, orless than 0.29. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C20 to total C20 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C21 to total C21 weight ratio less than0.37. Alternatively, the condensable hydrocarbon portion may have anormal-C21 to total C21 weight ratio less than 0.35, less than 0.32, orless than 0.30. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C21 to total C21 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C22 to total C22 weight ratio less than0.38. Alternatively, the condensable hydrocarbon portion may have anormal-C22 to total C22 weight ratio less than 0.36, less than 0.34, orless than 0.30. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C22 to total C22 weight ratio greater than0.10 or greater than 0.15. In some embodiments the condensablehydrocarbon portion has a normal-C23 to total C23 weight ratio less than0.43. Alternatively, the condensable hydrocarbon portion may have anormal-C23 to total C23 weight ratio less than 0.40, less than 0.35, orless than 0.29. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C23 to total C23 weight ratio greater than0.15 or greater than 0.20. In some embodiments the condensablehydrocarbon portion has a normal-C24 to total C24 weight ratio less than0.48. Alternatively, the condensable hydrocarbon portion may have anormal-C24 to total C24 weight ratio less than 0.46, less than 0.42, orless than 0.40. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C24 to total C24 weight ratio greater than0.15 or greater than 0.20. In some embodiments the condensablehydrocarbon portion has a normal-C25 to total C25 weight ratio less than0.48. Alternatively, the condensable hydrocarbon portion may have anormal-C25 to total C25 weight ratio less than 0.46, less than 0.42, orless than 0.40. In alternative embodiments, the condensable hydrocarbonportion may have a normal-C25 to total C25 weight ratio greater than0.20 or greater than 0.25. Certain features of the present invention aredescribed in terms of a set of numerical upper limits (e.g. “less than”)and a set of numerical lower limits (e.g. “greater than”) in thepreceding paragraph. It should be appreciated that ranges formed by anycombination of these limits are within the scope of the invention unlessotherwise indicated. The embodiments described in this paragraph may becombined with any of the other aspects of the invention discussedherein.

The use of “total C_” (e.g., total C10) herein and in the claims ismeant to refer to the amount of a particular pseudo component found in acondensable hydrocarbon fluid determined as described herein,particularly as described in the section labeled “Experiments” herein.That is “total C_” is determined using the whole oil gas chromatography(WOGC) analysis methodology according to the procedure described in theExperiments section of this application. Further, “total C_” isdetermined from the whole oil gas chromatography (WOGC) peak integrationmethodology and peak identification methodology used for identifying andquantifying each pseudo-component as described in the Experimentssection herein. Further, “total C_” weight percent and mole percentvalues for the pseudo components were obtained using the pseudocomponent analysis methodology involving correlations developed by Katzand Firoozabadi (Katz, D. L., and A. Firoozabadi, 1978. Predicting phasebehavior of condensate/crude-oil systems using methane interactioncoefficients, J. Petroleum Technology (November 1978), 1649-1655) asdescribed in the Experiments section, including the exemplary molar andweight percentage determinations.

The use of “normal-C_” (e.g., normal-C10) herein and in the claims ismeant to refer to the amount of a particular normal alkane hydrocarboncompound found in a condensable hydrocarbon fluid determined asdescribed herein, particularly in the section labeled “Experiments”herein. That is “normal-C_” is determined from the GC peak areasdetermined using the whole oil gas chromatography (WOGC) analysismethodology according to the procedure described in the Experimentssection of this application. Further, “total C_” is determined from thewhole oil gas chromatography (WOGC) peak identification and integrationmethodology used for identifying and quantifying individual compoundpeaks as described in the Experiments section herein. Further,“normal-C_” weight percent and mole percent values for the normal alkanecompounds were obtained using methodology analogous to the pseudocomponent exemplary molar and weight percentage determinations explainedin the Experiments section, except that the densities and molecularweights for the particular normal alkane compound of interest were usedand then compared to the totals obtained in the pseudo componentmethodology to obtain weight and molar percentages.

The following discussion of FIG. 16 concerns data obtained in Examples1-5 which are discussed in the section labeled “Experiments”. The datawas obtained through the experimental procedures, gas sample collectionprocedures, hydrocarbon gas sample gas chromatography (GC) analysismethodology, and gas sample GC peak identification and integrationmethodology discussed in the Experiments section. For clarity, whenreferring to gas chromatograms of gaseous hydrocarbon samples, graphicaldata is provided for one unstressed experiment through Example 1, two400 psi stressed experiments through Examples 2 and 3, and two 1,000 psistressed experiments through Examples 4 and 5.

FIG. 16 is a bar graph showing the concentration, in molar percentage,of the hydrocarbon species present in the gas samples taken from each ofthe three stress levels tested and analyzed in the laboratoryexperiments discussed herein. The gas compound molar percentages wereobtained through the experimental procedures, gas sample collectionprocedures, hydrocarbon gas sample gas chromatography (GC) analysismethodology, gas sample GC peak integration methodology and molarconcentration determination procedures described herein. For clarity,the hydrocarbon molar percentages are taken as a percentage of the totalof all identified hydrocarbon gas GC areas (i.e., methane, ethane,propane, iso-butane, n-butane, iso-pentane, n-pentane, 2-methyl pentane,and n-hexane) and calculated molar concentrations. Thus the graphedmethane to normal C6 molar percentages for all of the experiments do notinclude the molar contribution of any associated non-hydrocarbon gasphase product (e.g., hydrogen, CO₂ or H₂S), any of the unidentifiedhydrocarbon gas species listed in Tables 2, 4, 5, 7, or 9 (e.g., peaknumbers 2, 6, 8-11, 13, 15-22, 24-26, and 28-78 in Table 2) or any ofthe gas species dissolved in the liquid phase which were separatelytreated in the liquid GC's. The y-axis 3080 represents the concentrationin terms of molar percent of each gaseous compound in the gas phase. Thex-axis 3081 contains the identity of each hydrocarbon compound frommethane to normal hexane. The bars 3082A-I represent the molarpercentage of each gaseous compound for the unstressed experiment ofExample 1. That is 3082A represents methane, 3082B represents ethane,3082C represents propane, 3082D represents iso-butane, 3082E representsnormal butane, 3082F represents iso-pentane, 3082G represents normalpentane, 3082H represents 2-methyl pentane, and 3082I represents normalhexane. The bars 3083A-I and 3084A-I represent the molar percent of eachgaseous compound for samples from the duplicate 400 psi stressedexperiments of Examples 2 and 3, with the letters assigned in the mannerdescribed for the unstressed experiment. While the bars 3085A-I and3086A-I represent the molar percent of each gaseous compound for theduplicate 1,000 psi stressed experiments of Examples 4 and 5, with theletters assigned in the manner described for the unstressed experiment.From FIG. 16 it can be seen that the hydrocarbon gas produced in all theexperiments is primarily methane, ethane and propane on a molar basis.It is further apparent that the unstressed experiment, represented bybars 3082A-I, contains the most methane 3082A and least propane 3082C,both as compared to the 400 psi stress experiments hydrocarbon gases andthe 1,000 psi stress experiments hydrocarbon gases. Looking now at bars3083A-I and 3084A-I, it is apparent that the intermediate level 400 psistress experiments produced a hydrocarbon gas having methane 3083A &3084A and propane 3083C & 3084C concentrations between the unstressedexperiment represented by bars 3082A & 3082C and the 1,000 psi stressedexperiment represented by bars 3085A & 3085C and 3086A & 3086C. Lastly,it is apparent that the high level 1,000 psi stress experiments producedhydrocarbon gases having the lowest methane 3085A & 3086A concentrationand the highest propane concentrations 3085C & 3086C, as compared toboth the unstressed experiments represented by bars 3082A & 3082C andthe 400 psi stressed experiment represented by bars 3083A & 3084A and3083C & 3084C. Thus pyrolizing oil shale under increasing levels oflithostatic stress appears to produce hydrocarbon gases havingdecreasing concentrations of methane and increasing concentrations ofpropane.

The hydrocarbon fluid produced from the organic-rich rock formation mayinclude both a condensable hydrocarbon portion (e.g. liquid) and anon-condensable hydrocarbon portion (e.g. gas). In some embodiments thenon-condensable hydrocarbon portion includes methane and propane. Insome embodiments the molar ratio of propane to methane in thenon-condensable hydrocarbon portion is greater than 0.32. In alternativeembodiments, the molar ratio of propane to methane in thenon-condensable hydrocarbon portion is greater than 0.34, 0.36 or 0.38.As used herein “molar ratio of propane to methane” is the molar ratiothat may be determined as described herein, particularly as described inthe section labeled “Experiments” herein. That is “molar ratio ofpropane to methane” is determined using the hydrocarbon gas sample gaschromatography (GC) analysis methodology, gas sample GC peakidentification and integration methodology and molar concentrationdetermination procedures described in the Experiments section of thisapplication.

In some embodiments the condensable hydrocarbon portion of thehydrocarbon fluid includes benzene. In some embodiments the condensablehydrocarbon portion has a benzene content between 0.1 and 0.8 weightpercent. Alternatively, the condensable hydrocarbon portion may have abenzene content between 0.15 and 0.6 weight percent, a benzene contentbetween 0.15 and 0.5, or a benzene content between 0.15 and 0.5.

In some embodiments the condensable hydrocarbon portion of thehydrocarbon fluid includes cyclohexane. In some embodiments thecondensable hydrocarbon portion has a cyclohexane content less than 0.8weight percent. Alternatively, the condensable hydrocarbon portion mayhave a cyclohexane content less than 0.6 weight percent or less than0.43 weight percent. Alternatively, the condensable hydrocarbon portionmay have a cyclohexane content greater than 0.1 weight percent orgreater than 0.2 weight percent.

In some embodiments the condensable hydrocarbon portion of thehydrocarbon fluid includes methyl-cyclohexane. In some embodiments thecondensable hydrocarbon portion has a methyl-cyclohexane content greaterthan 0.5 weight percent. Alternatively, the condensable hydrocarbonportion may have a methyl-cyclohexane content greater than 0.7 weightpercent or greater than 0.75 weight percent. Alternatively, thecondensable hydrocarbon portion may have a methyl-cyclohexane contentless than 1.2 or 1.0 weight percent.

The use of weight percentage contents of benzene, cyclohexane, andmethyl-cyclohexane herein and in the claims is meant to refer to theamount of benzene, cyclohexane, and methyl-cyclohexane found in acondensable hydrocarbon fluid determined as described herein,particularly as described in the section labeled “Experiments” herein.That is, respective compound weight percentages are determined from thewhole oil gas chromatography (WOGC) analysis methodology and whole oilgas chromatography (WOGC) peak identification and integrationmethodology discussed in the Experiments section herein. Further, therespective compound weight percentages were obtained as described forFIG. 11, except that each individual respective compound peak areaintegration was used to determine each respective compound weightpercentage. For clarity, the compound weight percentages are taken as apercentage of the entire C3 to pseudo C38 whole oil gas chromatographyareas and calculated weights as used in the pseudo compound datapresented in FIG. 7.

In some embodiments the condensable hydrocarbon portion of thehydrocarbon fluid has an API gravity greater than 30. Alternatively, thecondensable hydrocarbon portion may have an API gravity greater than 30,32, 34, 36, 40, 42 or 44. As used herein and in the claims, API gravitymay be determined by any generally accepted method for determining APIgravity.

In some embodiments the condensable hydrocarbon portion of thehydrocarbon fluid has a basic nitrogen to total nitrogen ratio between0.1 and 0.50. Alternatively, the condensable hydrocarbon portion mayhave a basic nitrogen to total nitrogen ratio between 0.15 and 0.40. Asused herein and in the claims, basic nitrogen and total nitrogen may bedetermined by any generally accepted method for determining basicnitrogen and total nitrogen. Where results conflict, the generallyaccepted more accurate methodology shall control.

One embodiment of the invention includes an in situ method of producinghydrocarbon fluids with improved properties from an organic-rich rockformation. Applicants have surprisingly discovered that the quality ofthe hydrocarbon fluids produced from in situ heating and pyrolysis of anorganic-rich rock formation may be improved by selecting sections of theorganic-rich rock formation with a certain lithostatic stress for insitu heating and pyrolysis. Further, applicants have discovered that thetemperature at which the in situ pyrolysis is accomplished has an effecton the composition of the produced fluid, that the effect of increasingtemperature generally affects the composition of the produced fluid inthe same direction as increasing lithostatic stress, and that the effectof decreasing temperature generally affects the composition of theproduced fluid in the same direction as decreasing lithostatic stress.Further, applicants have discovered that the pressure at which the insitu pyrolysis is conducted affects the composition of the producedfluid, that the compositional effect of increasing pressure is generallyin a direction opposite to the effects of lithostatic stress andtemperature and that the compositional effect of pressure is generallyof a much lower magnitude than the effects of temperature andlithostatic stress.

The method may include creating the hydrocarbon fluid by pyrolysis of asolid hydrocarbon and/or a heavy hydrocarbon present in the organic-richrock formation. Embodiments may include the hydrocarbon fluid beingpartially, predominantly or substantially completely created bypyrolysis of the solid hydrocarbon and/or heavy hydrocarbon present inthe organic-rich rock formation.

Applicants have found that in situ heating and pyrolysis of organic-richrock formations with differing amounts of stress lead to the productionof hydrocarbon fluids with changed properties. The method may include insitu heating of a section of the organic-rich rock formation that has aselected lithostatic stress to form hydrocarbon fluids with desiredproperties. Selecting or maintaining a higher lithostatic stress willincrease the production of aromatic and cyclic hydrocarbon compounds,while decreasing the production of normal and isoprenoid (or branched)hydrocarbon compounds. Alternatively, maintaining a lower lithostaticstress will decrease the production of aromatic and cyclic hydrocarboncompounds, while increasing the production of normal and isoprenoid (orbranched) hydrocarbon compounds. The method may include heating in situa section of the organic-rich rock formation having a lithostatic stressgreater than 200 psi and producing a hydrocarbon fluid from the heatedsection of the organic-rich rock formation. In alternative embodiments,the heated section of the organic-rich rock formation may have alithostatic stress greater than 400 psi. In alternative embodiments, theheated section of the organic-rich rock formation may have a lithostaticstress greater than 800 psi, greater than 1,000 psi, greater than 1,200psi, greater than 1,500 psi or greater than 2,000 psi depending on thecomposition desired. In alternative embodiments, the heated section ofthe organic-rich rock formation may have a lithostatic stress less than800 psi, less than 1,000 psi, less than 1,500 psi, less than 2,500 psior less than 3,000 psi depending on the composition desired. Inalternative embodiments, the heated section of the organic-rich rockformation may have a lithostatic stress between 200 psi and 1,000 psi,between 200 psi and 900 psi, between 200 psi and 800 psi, between 200psi and 700 psi or between 200 psi and 600 psi depending on thecomposition desired. In alternative embodiments, the heated section ofthe organic-rich rock formation may have a lithostatic stress between800 psi and 3,000 psi, between 900 psi and 3,000 psi, between 1,000 psiand 3,000 psi, between 1,200 psi and 3,000 psi or between 1,500 psi and3,000 psi depending on the composition desired.

Further, the method may include controlling the temperature or range oftemperatures the section of the organic-rich rock formation experiencesin order to effect the composition of the produced hydrocarbon fluids.For example, the heating rate of sources of in situ heat may be set oradjusted to affect the temperature profile of the section of theorganic-rich rock formation. Further, the density or configuration ofthe sources of in situ heat may be implemented or adjusted to effect thecomposition of the produced hydrocarbon fluid. Higher temperatures willfavor the production of aromatics and cyclic hydrocarbon compounds,while lower temperatures will favor the production of normal andisoprenoid (or branched) hydrocarbon compounds. Alternatively, lowertemperatures will tend to decrease aromatic and cyclic hydrocarboncompound production while higher temperatures will tend to decreaseproduction of normal and isoprenoid (or branched) hydrocarbon compounds.Thus, the method may include heating a section of the organic-rich rockformation to a maximum temperature above 270° C. Alternatively, themethod may include heating the section of the organic-rich rockformation to a maximum temperature between 270° C. and 600° C., between270° C. to 550° C., between 270° C. to 500° C., between 270° C. to 450°C., between 270° C. to 400° C. or between 270° C. to 350° C. dependingon the composition desired. Alternatively, the method may includeheating the section of the organic-rich rock formation to a maximumtemperature between 350° C. and 500° C., between 350° C. to 550° C.,between 350° C. to 600° C., between 350° C. to 650° C., between 350° C.to 700° C. or between 350° C. to 750° C. depending on the compositiondesired. The method may include heating the section of the organic-richrock formation by any method, including any of the methods describedherein. For example, the method may include heating the section of theorganic-rich rock formation by electrical resistance heating. Further,the method may include heating the section of the organic-rich rockformation through use of a heated heat transfer fluid.

Further, the method may include maintaining a range of pressures in thesection of the organic-rich rock formation in order to effect thecomposition of the produced hydrocarbon fluid. One method of maintaininga range of pressures in the section of the organic-rich rock formationincludes selecting the section by estimating the section's lithostaticstress in order to limit the maximum pressure that such a section islikely to experience by relying on the creation of fractures to relievethe pressure force due to in situ heating. The effect of pressure whencombined with lithostatic stress will tend to alter the effect oflithostatic stress on the composition of the produced fluid. Lowerpressures when combined with lithostatic stress will tend to enhanceproduction of aromatic and cyclic hydrocarbon compounds and decreaseproduction of normal and isoprenoid (or branched) hydrocarbon compounds.Alternatively, higher pressures when combined with lithostatic stresswill tend to incrementally reduce production of aromatic and cyclichydrocarbon compounds and increase production of normal and isoprenoid(or branched) hydrocarbon compounds. Thus, the method may includemaintaining the pressure of a heated section of an organic-rich rockformation above 200 psig and producing a hydrocarbon fluid from theheated section of the organic-rich rock formation. In alternativeembodiments, the method may include maintaining the pressure of a heatedsection of the organic-rich rock formation below 3,000 psig. Inalternative embodiments, the method may include maintaining the pressureof a heated section of the organic-rich rock formation below 2,500 psig,below 2,000 psig, below 2,500 psig, below 2,000 psig or below 1,500 psigdepending on the composition desired. In alternative embodiments, themethod may include allowing the pressure of a heated section of theorganic-rich rock formation to reach a maximum pressure above 400 psig,above 500 psig, above 800 psig, above 1,000 psig, above 1,500 psig orabove 2,000 psig depending on the composition desired. In alternativeembodiments, the method may include allowing the pressure of a heatedsection of the organic-rich rock formation to reach a maximum pressurebetween 200 psig and 1,000 psig, between 200 psig and 900 psig, between200 psig and 800 psig, between 200 psig and 700 psig or between 200 psigand 600 psig depending on the composition desired. In alternativeembodiments, the method may include allowing the pressure of a heatedsection of the organic-rich rock formation to reach a maximum pressurebetween 800 psig and 3,000 psig, between 900 psig and 3,000 psig,between 1,000 psig and 3,000 psig, between 1,200 psig and 3,000 psig orbetween 1,500 psig and 3,000 psig depending on the composition desired.

The organic-rich rock formation may be, for example, a heavy hydrocarbonformation or a solid hydrocarbon formation. Particular examples of suchformations may include an oil shale formation, a tar sands formation ora coal formation. Particular formation hydrocarbons present in suchformations may include oil shale, kerogen, coal, and/or bitumen.

The hydrocarbon fluid produced from the organic-rich rock formation mayinclude both a condensable hydrocarbon portion (e.g. liquid) and anon-condensable hydrocarbon portion (e.g. gas). The hydrocarbon fluidmay additionally be produced together with non-hydrocarbon fluids.Exemplary non-hydrocarbon fluids include, for example, water, carbondioxide, hydrogen sulfide, hydrogen, ammonia, and/or carbon monoxide.

The condensable hydrocarbon portion of the hydrocarbon fluid may be afluid present within different locations associated with an organic-richrock development project. For example, the condensable hydrocarbonportion of the hydrocarbon fluid may be a fluid present within aproduction well that is in fluid communication with the organic-richrock formation. The production well may serve as a device forwithdrawing the produced hydrocarbon fluids from the organic-rich rockformation. Alternatively, the condensable hydrocarbon portion may be afluid present within processing equipment adapted to process hydrocarbonfluids produced from the organic-rich rock formation. Exemplaryprocessing equipment is described herein. Alternatively, the condensablehydrocarbon portion may be a fluid present within a fluid storagevessel. Fluid storage vessels may include, for example, fluid storagetanks with fixed or floating roofs, knock-out vessels, and otherintermediate, temporary or product storage vessels. Alternatively, thecondensable hydrocarbon portion may be a fluid present within a fluidtransportation pipeline. A fluid transportation pipeline may include,for example, piping from production wells to processing equipment orfluid storage vessels, piping from processing equipment to fluid storagevessels, or pipelines associated with collection or transportation offluids to or from intermediate or centralized storage locations.

The following discussion of FIGS. 29-38 concerns data obtained inExamples 6-19 which are discussed in the section labeled “Experiments”.The data was obtained through the experimental procedures, gas andliquid sample collection procedures, C4-C19 liquid sample gaschromatography (C4-C19 GC) analysis methodology, and C4-C19 liquidsample gas chromatography (C4-C19 GC) peak integration methodologydiscussed in the Experiments section. For clarity, when referring toC4-C19 liquid sample gas chromatography (C4-C19 GC) chromatograms ofliquid hydrocarbon samples, graphical data is provided for Examples 6-19in FIGS. 29-52 while peak area information may be found in Table 16 inthe Experiments section.

FIG. 29 is a graph of the weight ratio of each identified compoundoccurring from n-C4 to n-C19 for each of the six 393° C. experimentstested and analyzed in the laboratory experiments (Examples 13-19)discussed herein compared to the weight ratio of each identifiedcompound occurring from n-C4 to n-C19 for Example 13 conducted at 393°C., 500 psig initial argon pressure and 0 psi stress. The compoundweight ratios were obtained through the experimental procedures, liquidsample collection procedures, C4-C19 liquid sample gas chromatography(C4-C19 GC) analysis methodology, C4-C19 gas chromatography peakidentification and integration methodology, and C4-C19 compound analysismethodology discussed in the Experiments section. For clarity, thecompound weight ratios were derived as a ratio of a particularcompound's percentage of the total peak area in one experiment to thesame compound's percentage of the total peak area for the 393/500/0experiment (Experiment 13). When referring to experimental conditionsherein, the notational format “Temperature (° C.)/Initial Argon Pressure(psig)/Stress load (psi)” will be used as a shorthand to refer to thetemperature, initial argon pressure and stress loading of a particularexperiment. For example, the notation “393/500/0” refers to anexperiment conducted at 393° C., 500 psig initial argon pressure and 0psi stress load as present in Example 13. Thus the graphed n-C4 to n-C19weight ratios do not include the weight contribution of the associatedgas phase product from any of the experiments. Further, the graphedweight ratios do not include the weight contribution of any liquidhydrocarbon compounds heavier than (i.e. having a longer retention timethan) n-C19 or any unidentified (i.e., not listed in FIG. 29 or Table16) compounds from the C4-C19 GC data. The y-axis 220 represents theweight ratio of a particular compound for a given experiment to the samecompound for the 393/500/0 experiment (Experiment 13). The x-axis 221contains the identity of each identified compound from n-C4 to n-C19.The data points occurring on line 222 represent the weight ratio of eachidentified n-C4 to n-C19 compound for the 393/500/400 experiment ofExample 15 to the 393/500/0 experiment of Experiment 13. The data pointsoccurring on line 223 represent the weight ratio of each identified n-C4to n-C19 compound for the 393/500/1000 experiment of Example 18 to the393/500/0 experiment of Experiment 13. The data points occurring on line224 represent the weight ratio of each identified n-C4 to n-C19 compoundfor the 393/200/400 experiment of Example 16 to the 393/500/0 experimentof Experiment 13. The data points occurring on line 225 represent theweight ratio of each identified n-C4 to n-C19 compound for the393/200/1000 experiment of Example 19 to the 393/500/0 experiment ofExperiment 13. The data points occurring on line 226 represent theweight ratio of each identified n-C4 to n-C19 compound for the 393/200/0experiment of Example 14 to the 393/500/0 experiment of Experiment 13.The data points occurring on line 227 represent the weight ratio of eachidentified n-C4 to n-C19 compound for the 393/50/400 experiment ofExample 17 to the 393/500/0 experiment of Experiment 13.

From FIG. 29 it can be seen that the hydrocarbon liquids produced in thetwo 1,000 psi stressed experiments, represented by data points on line223 & 225, generally contain an increased weight ratio of aromatichydrocarbon compounds, including for example benzene (Bz), toluene(Tol), ethylbenzene (EBz), ortho-xylene (oXyl), meta-xylene (mXyl),1-ethyl-3-methylbenzene (1E3 MBz), 1-ethyl-4-methylbenzene (1E4 MBz),1,2,4-trimethylbenzene (1-2-4TMBz), 1-ethyl-2,3-dimethylbenzene(1E2-3DMBz), tetralin, 2-methylnaphthalene (2MNaph), 1-methylnaphthalene(1MNaph). It also can be seen that for the two 1,000 psi stressexperiments, the lower initial argon pressure (200 psig argon)experiment represented by line 225 is generally more enriched inaromatic compounds relative to the higher initial argon pressure (500psig argon) experiment represented by line 223. From FIG. 29 it can alsobe seen that the hydrocarbon liquids produced in the three 400 psistressed experiments, represented by data points on line 222, 224 & 227,generally contain an increased weight ratio of aromatic hydrocarboncompounds relative to the unstressed experiments (i.e., line 226 & the“1” line on the y-axis representing Experiments 13 & 14) but a lowerweight ratio of aromatic hydrocarbon compounds relative to the 1,000 psistressed experiments (Lines 223 & 225). It also can be seen that for thethree 400 psi stress experiments, the lowest initial argon pressure (50psig argon) experiment represented by line 227 is generally moreenriched in aromatic compounds relative to the middle initial argonpressures (200 psig argon) experiment represented by line 224 and thehighest initial argon pressures (500 psig argon) experiment representedby line 222, with the middle initial argon pressures (200 psig argon)experiment represented by line 224 generally falling between the highestand lowest initial argon pressure experiments. Thus pyrolyzing oil shaleunder increasing levels of stress appears to enrich the producedhydrocarbon liquid in aromatic compounds while decreasing pressureappears to enhance aromatic compound production.

From FIG. 29 it can also be seen that the hydrocarbon liquids producedin the two 1,000 psi stressed experiments, represented by data points online 223 & 225, generally contain an increased weight ratio of cyclichydrocarbon compounds, including for example cis 1,3-dimethylcyclopentane (c1-3DMCyC5), trans 1,3-dimethyl cyclopentane (t1-3DMCyC5),trans 1,2-dimethyl cyclopentane (t1-2DMCyC5), methyl cyclohexane(MCyC6), ethyl cyclopentane (ECyC5), 1,1-dimethyl cyclohexane(1-1DMCyC6), trans 1,2-dimethyl cyclohexane (1-1DMCyC6), and ethylcyclohexane (ECyC6). It also can be seen that for the two 1,000 psistress experiments, the lower initial argon pressure (200 psig argon)experiment represented by line 225 is generally more enriched in cycliccompounds relative to the higher initial argon pressure (500 psig argon)experiment represented by line 223. From FIG. 29 it can also be seenthat the hydrocarbon liquid produced in the three 400 psi stressedexperiments, represented by data points on line 222, 224 & 227,generally contain an increased weight ratio of cyclic hydrocarboncompounds relative to the unstressed experiments (i.e., line 226 & the“1” line on the y-axis representing Experiments 13 & 14) but a lowerweight ratio of cyclic hydrocarbon compounds relative to the 1,000 psistressed experiments (Lines 223 & 225). It also can be seen that for thethree 400 psi stress experiments, the lowest initial argon pressure (50psig argon) experiment represented by line 227 is generally moreenriched in cyclic compounds relative to the middle initial argonpressures (200 psig argon) experiment represented by line 224 and thehighest initial argon pressures (500 psig argon) experiment representedby line 222, with the middle initial argon pressures (200 psig argon)experiment represented by line 224 generally falling between the highestand lowest initial argon pressure experiments. Thus pyrolyzing oil shaleunder increasing levels of stress appears to enrich the producedhydrocarbon liquid in cyclic hydrocarbon compounds while decreasingpressure appears to enhance cyclic hydrocarbon compound production.

From FIG. 29 it can also be seen that the hydrocarbon liquids producedin the two 1,000 psi stressed experiments, represented by data points online 223 & 225, generally contain a decreased weight ratio of normalalkane hydrocarbon compounds for n-C8 and heavier normal alkanehydrocarbon compounds, including for example n-C9 through n-C19. It alsocan be seen that for the two 1,000 psi stress experiments, the lowerinitial argon pressure (200 psig argon) experiment represented by line225 is generally more depleted of normal hydrocarbon compounds relativeto the higher initial argon pressure (500 psig argon) experimentrepresented by line 223. From FIG. 29 it can also be seen that thehydrocarbon liquid produced in the three 400 psi stressed experiments,represented by data points on line 222, 224 & 227, generally contain adecreased weight amount of normal hydrocarbon compounds relative to theunstressed experiments (i.e., line 226 & the “1” line on the y-axisrepresenting Experiments 13 & 14) but a less depleted weight ratio ofnormal hydrocarbon compounds relative to the 1,000 psi stressedexperiments (Lines 223 & 225). It also can be seen that for the three400 psi stress experiments, the lowest initial argon pressure (50 psigargon) experiment represented by line 227 is generally more depleted ofnormal compounds relative to the middle initial argon pressures (200psig argon) experiment represented by line 224 and the highest initialargon pressures (500 psig argon) experiment represented by line 222,with the middle initial argon pressures (200 psig argon) experimentrepresented by line 224 generally falling between the highest and lowestinitial argon pressure experiments. Thus pyrolyzing oil shale underincreasing levels of stress appears to deplete the produced hydrocarbonliquid in normal hydrocarbon compounds while decreasing pressure alsoappears to decrease normal hydrocarbon compound production.

From FIG. 29 it can also be seen that the hydrocarbon liquids producedin the two 1,000 psi stressed experiments, represented by data points online 223 & 225, generally contain a decreased weight ratio of isoprenoidhydrocarbon compounds, including for example IP-9, IP-10, IP-11, IP-13,IP-14, IP-16, IP-18, pristane and phytane. It also can be seen that forthe two 1,000 psi stress experiments, the lower initial argon pressure(200 psig argon) experiment represented by line 225 is generally moredepleted of isoprenoid hydrocarbon compounds relative to the higherinitial argon pressure (500 psig argon) experiment represented by line223. From FIG. 29 it can also be seen that the hydrocarbon liquidproduced in the three 400 psi stressed experiments, represented by datapoints on line 222, 224 & 227, generally contain a decreased weightamount of isoprenoid hydrocarbon compounds relative to the unstressedexperiments (i.e., line 226 & the “1” line on the y-axis representingExperiment 13 & 14) but a less depleted weight ratio of isoprenoidhydrocarbon compounds relative to the 1,000 psi stressed experiments(Lines 223 & 225). It also can be seen that for the three 400 psi stressexperiments, the lowest initial argon pressure (50 psig argon)experiment represented by line 227 is generally more depleted ofisoprenoid compounds relative to the middle initial argon pressures (200psig argon) experiment represented by line 224 and the highest initialargon pressures (500 psig argon) experiment represented by line 222,with the middle initial argon pressures (200 psig argon) experimentrepresented by line 224 generally falling between the highest and lowestinitial argon pressure experiments. Thus pyrolyzing oil shale underincreasing levels of stress appears to deplete the produced hydrocarbonliquid in isoprenoid hydrocarbon compounds while decreasing pressurealso appears to decrease isoprenoid hydrocarbon compound production.

Isoprenoid hydrocarbon compounds are hydrocarbon compounds based on theisoprene structure. They are constructed by linking 2 or more 5 carbonisoprene units together building molecules with up to 40 or more carbonatoms. Isoprene is a diolefin but the double bonds are typicallysaturated during diagenesis so compounds built up from isoprene unitsare referred to as isoprenoids. Although the 5 carbon isoprene unitimplies that isoprenoids should contain carbons in multiples of 5 thisis not the case as carbons can be cleaved off during diagenesis. The useof “IP-_” (e.g., IP-10) herein and in the claims is meant to refer to ahydrocarbon structure based on isoprene with the number following thehyphen denoting the carbon number of a particular isoprenoid. Forexample, IP-10 means a hydrocarbon structure based on isoprene having 10carbon atoms.

FIG. 30 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 393° C. experimental data discussed in Examples 13-19 inthe Experimental section herein. The compound weight ratios wereobtained through the experimental procedures, sample collection andanalytical techniques discussed above for FIG. 29 and in the Experimentssection. Except that, the normal hydrocarbon compound to aromatichydrocarbon compound weight ratios are derived as a ratio of aparticular normal hydrocarbon compound's peak area in one experiment toa particular aromatic hydrocarbon compound's peak area for the sameparticular experiment. Thus the graphed weight ratios represent a weightratio of two different compounds produced in the same experiment. They-axis 230 represents the weight ratio of two compounds for a givenexperiment. The x-axis 231 contains the identity of each depictedcompound ratio. The bars 232 a-g represent the weight ratio ofn-C6/benzene (n-C6/Bnz). The bars 233 a-g represent the weight ratio ofn-C7/toluene (n-C7/Tol). The bars 234 a-g represent the weight ratio ofn-C8/ethylbenzene (n-C8/EB). The bars 235 a-g represent the weight ratioof n-C8/ortho-xylene (n-C8/o-xyl). The bars 236 a-g represent the weightratio of n-C8/meta-xylene (n-C8/m-xyl). The bars 237 a-g represent theweight ratio of n-C9/1-ethyl-3-methylbenzene (1E3M Bnz). The bars 238a-g represent the weight ratio of n-C9/1-ethyl-4-methylbenzene(n-C9/1E4M Bnz). The bars 239 a-g represent the weight ratio ofn-C9/1,2,4-trimethylbenzene (n-C9/1,2,4TM Bnz). The bars 240 a-grepresent the weight ratio of n-C10/1-ethyl-2,3-dimethylbenzene(n-C10/1E 2,3DM Bnz). The bars 241 a-g represent the weight ratio ofn-C10/tetralin. The bars 242 a-g represent the weight ratio ofn-C12/2-methylnaphthalene (n-C12/2M Naph). The bars 243 a-g representthe weight ratio of n-C12/1-methylnaphthalene (n-C12/1M Naph). For eachof the compound ratio groups, the “a” designation denotes the 393/500/0experiment, the “b” designation denotes the 393/200/0 experiment, the“c” designation denotes the 393/500/400 experiment, the “d” designationdenotes the 393/200/400 experiment, the “e” designation denotes the393/50/400 experiment, the “f” designation denotes the 393/500/1000experiment, while the “g” designation denotes the 393/200/1000experiment.

From FIG. 30 it can be seen that the hydrocarbon liquids produced in thetwo 1,000 psi stressed experiments, represented by the “f” and “g” barsof 232-243, generally contain the most respective aromatic hydrocarboncompounds, including for example benzene, toluene, ethylbenzene,ortho-xylene, meta-xylene, 1-ethyl-3-methylbenzene,1-ethyl-4-methylbenzene, 1,2,4-trimethylbenzene,1-ethyl-2,3-dimethylbenzene, tetralin, 2-methylnaphthalene, and1-methylnaphthalene, relative to the respective corresponding samecarbon number normal hydrocarbon compound. It also can be seen that forthe two 1,000 psi stress experiments, the lower initial argon pressure(200 psig argon) experiment represented by the “g” bars is generallymore enriched in aromatic compounds relative to the higher initial argonpressure (500 psig argon) experiment represented by the “f” bars. FromFIG. 30 it can also be seen that the hydrocarbon liquids produced in thethree 400 psi stressed experiments, represented by the “c”, “d” and “f”bars, generally contain an increased amount of aromatic hydrocarboncompounds relative to the unstressed experiments (i.e., bars “a” and“b”) but a lower amount of aromatic hydrocarbon compounds relative tothe 1,000 psi stressed experiments (bars “f” and “g”). It also can beseen that for the three 400 psi stress experiments, the lowest initialargon pressure (50 psig argon) experiment represented by the “e” bars isgenerally more enriched in aromatic compounds relative to the middleinitial argon pressures (200 psig argon) experiment represented by the“d” bars and the highest initial argon pressures (500 psigg argon)experiment represented by the “c” bars, with the middle initial argonpressures (200 psig argon) experiment represented the “d” bars generallyfalling between the highest and lowest initial argon pressureexperiments. By comparing the effect of the 0, 400, and 1,000 psistressed data at consistent initial argon pressures (i.e., the a, c, andf data all at 500 psig initial argon or the b, d, and g data all at 200psig initial argon) to the three 400 psi stress at different initialargon pressures data (i.e., the c, d, and e data), it becomes apparentthat the compositional changes due to step changes in stress (i.e., 0psi to 400 psi and 400 psi to 1,000 psi) are much more pronounced thanthe compositional changes due to step changes in pressure (i.e., 50 psigto 200 psig and 200 psig to 500 psig). It is also noted that the effectof increased pressure appears to partially retard the effect ofincreased stress. Thus pyrolyzing oil shale under increasing levels ofstress appears to enrich the produced hydrocarbon liquid in aromaticcompounds while decreasing pressure appears to enhance aromatic compoundproduction. Further, the magnitude of compositional changed due tochanges in stress appears to be more significant than the magnitude ofthe compositional change due to changes in pressure.

FIG. 31 is a bar graph of the weight ratio of the normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 375° C. experimental data discussed in Examples 6-12 in theExperimental section herein. The compound weight ratios were obtainedthrough the experimental procedures, sample collection and analyticaltechniques discussed above for FIG. 30 and in the Experiments section.For clarity, the normal hydrocarbon compound to aromatic hydrocarboncompound weight ratios are derived as a ratio of a particular normalhydrocarbon compound's peak area in one experiment to a particulararomatic hydrocarbon compound's peak area for the same particularexperiment. Thus the graphed weight ratios represent a weight ratio oftwo different compounds produced in the same experiment. The y-axis 250represents the weight ratio of two compounds for a given experiment. Thex-axis 251 contains the identity of each depicted compound ratio. Thebars 252 a-g represent the weight ratio of n-C6/benzene (n-C6/Bnz). Thebars 253 a-g represent the weight ratio of n-C7/toluene (n-C7/Tol). Thebars 254 a-g represent the weight ratio of n-C8/ethylbenzene (n-C8/EB).The bars 255 a-g represent the weight ratio of n-C8/ortho-xylene(n-C8/o-xyl). The bars 256 a-g represent the weight ratio ofn-C8/meta-xylene (n-C8/m-xyl). The bars 257 a-g represent the weightratio of n-C9/1-ethyl-3-methylbenzene (1E3M Bnz). The bars 258 a-grepresent the weight ratio of n-C9/1-ethyl-4-methylbenzene (n-C9/1E4MBnz). The bars 259 a-g represent the weight ratio ofn-C9/1,2,4-trimethylbenzene (n-C9/1,2,4TM Bnz). The bars 260 a-grepresent the weight ratio of n-C10/1-ethyl-2,3-dimethylbenzene(n-C10/1E 2,3DM Bnz). The bars 261 a-g represent the weight ratio ofn-C10/tetralin. The bars 262 a-g represent the weight ratio ofn-C12/2-methylnaphthalene (n-C12/2M Naph). The bars 263 a-g representthe weight ratio of n-C12/1-methylnaphthalene (n-C12/1M Naph). For eachof the compound ratio groups, the “a” designation denotes the 375/500/0experiment, the “b” designation denotes the 375/200/0 experiment, the“c” designation denotes the 375/500/400 experiment, the “d” designationdenotes the 375/200/400 experiment, the “e” designation denotes the375/50/400 experiment, the “f” designation denotes the 375/500/1000experiment, while the “g” designation denotes the 375/200/1000experiment.

From FIG. 31 it can be seen that the hydrocarbon liquids produced in thetwo 1,000 psi stressed experiments, represented by the “f” and “g” barsof 252-263, generally contain the most respective aromatic hydrocarboncompounds, including for example benzene, toluene, ethylbenzene,ortho-xylene, meta-xylene, 1-ethyl-3-methylbenzene,1-ethyl-4-methylbenzene, 1,2,4-trimethylbenzene,1-ethyl-2,3-dimethylbenzene, tetralin, 2-methylnaphthalene, and1-methylnaphthalene, relative to the respective corresponding samecarbon number normal hydrocarbon compound. It also can be seen that forthe two 1,000 psi stress experiments, the lower initial argon pressure(200 psig argon) experiment represented by the “g” bars is generallymore enriched in aromatic compounds relative to the higher initial argonpressure (500 psig argon) experiment represented by the “f” bars. FromFIG. 31 it can also be seen that the hydrocarbon liquids produced in thethree 400 psi stressed experiments, represented by the “c”, “d” and “f”bars, generally contain an increased amount of aromatic hydrocarboncompounds relative to the unstressed experiments (i.e., bars “a” and“b”) but a lower amount of aromatic hydrocarbon compounds relative tothe 1,000 psi stressed experiments (bars “f” and “g”). It also can beseen that for the three 400 psi stress experiments, the lowest initialargon pressure (50 psig argon) experiment represented by the “e” bars isgenerally more enriched in aromatic compounds relative to the middleinitial argon pressures (200 psig argon) experiment represented by the“d” bars and the highest initial argon pressures (500 psig argon)experiment represented by the “c” bars, with the middle initial argonpressures (200 psig argon) experiment represented the “d” bars generallyfalling between the highest and lowest initial argon pressureexperiments. While the ordering of the 375° C. data is not as consistentas the 393° C. data and magnitude of the differentiation between theratios for different experimental parameters is not as great for the375° C. data, the same general trends are apparent for the 375° C. dataas observed with respect to the 393° C. data. Thus pyrolyzing oil shaleunder increasing levels of stress at more moderate temperatures appearsto enrich the produced hydrocarbon liquid in aromatic compounds whiledecreasing pressure appears to enhance aromatic compound production.However, the trends are less consistent and less pronounced at thereduced temperature.

FIG. 32 is a bar graph of the weight ratio of the normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 375° C. and seven 393° C. experimental data discussed inExamples 6-19 in the Experimental section herein. The compound weightratios were obtained through the experimental procedures, samplecollection and analytical techniques discussed above for FIG. 30 and inthe Experiments section. For clarity, the normal hydrocarbon compound toaromatic hydrocarbon compound weight ratios are derived as a ratio of aparticular normal hydrocarbon compound's peak area in one experiment toa particular aromatic hydrocarbon compound's peak area for the sameparticular experiment. Thus the graphed weight ratios represent a weightratio of two different compounds produced in the same experiment. They-axis 270 represents the weight ratio of two compounds for a givenexperiment. The x-axis 271 contains the identity of each depictedcompound ratio. The bars 272 a-g represent the weight ratio ofn-C6/benzene (n-C6/Bnz) at 375° C. while the bars 272 a′-g′ representthe weight ratio of n-C6/benzene at 393° C. It can be seen that the 76.4value of bar 272 a exceeds the y-axis scale of 60.0. The bars 273 a-grepresent the weight ratio of n-C7/toluene (n-C7/Tol) at 375° C. whilethe bars 273 a′-g′ represent the weight ratio of n-C7/toluene at 393° C.The bars 274 a-g represent the weight ratio of n-C8/ethylbenzene(n-C8/EB) at 375° C. while the bars 274 a′-g′ represent the weight ratioof n-C8/ethylbenzene at 393° C. The bars 275 a-g represent the weightratio of n-C8/ortho-xylene (n-C8/o-xyl) at 375° C. while the bars 275a′-g′ represent the weight ratio of C8/ortho-xylene at 393° C. The bars276 a-g represent the weight ratio of n-C8/meta-xylene (n-C8/m-xyl) at375° C. while the bars 276 a′-g′ represent the weight ratio ofn-C8/meta-xylene at 393° C. The bars 277 a-g represent the weight ratioof n-C9/1-ethyl-3-methylbenzene (1E3M Bnz) at 375° C. while the bars 277a′-g′ represent the weight ratio of n-C9/1-ethyl-3-methylbenzene at 393°C. The bars 278 a-g represent the weight ratio ofn-C9/1-ethyl-4-methylbenzene (n-C9/1E4M Bnz) at 375° C. while the bars278 a′-g′ represent the weight ratio of n-C9/1-ethyl-4-methylbenzene at393° C. The bars 279 a-g represent the weight ratio ofn-C9/1,2,4-trimethylbenzene (n-C9/1,2,4TM Bnz) at 375° C. while the bars279 a′-g′ represent the weight ratio of n-C9/1,2,4-trimethylbenzene at393° C. The bars 280 a-g represent the weight ratio ofn-C10/1-ethyl-2,3-dimethylbenzene (n-C10/1E 2,3DM Bnz) at 375° C. whilethe bars 280 a′-g′ represent the weight ratio ofn-C10/1-ethyl-2,3-dimethylbenzene at 393° C. The bars 281 a-g representthe weight ratio of n-C10/tetralin at 375° C. while the bars 281 a′-g′represent the weight ratio of n-C10/tetralin at 393° C. The bars 282 a-grepresent the weight ratio of n-C12/2-methylnaphthalene (n-C12/2M Naph)at 375° C. while the bars 282 a′-g′ represent the weight ratio ofn-C12/2-methylnaphthalene at 393° C. The bars 283 a-g represent theweight ratio of n-C12/1-methylnaphthalene (n-C12/1M Naph) at 375° C.while the bars 283 a′-g′ represent the weight ratio ofn-C12/1-methylnaphthalene at 393° C. For each of the compound ratiogroups, the “a” designation denotes the 375/500/0 experiment, the “a′”designation denotes the 393/500/0 experiment, the “b” designationdenotes the 375/200/0 experiment, the “b′” designation denotes the393/200/0 experiment, the “c” designation denotes the 375/500/400experiment, the “c′” designation denotes the 393/500/400 experiment, the“d” designation denotes the 375/200/400 experiment, the “d′” designationdenotes the 393/200/400 experiment, the “e” designation denotes the375/50/400 experiment, the “e′” designation denotes the 393/50/400experiment, the “f” designation denotes the 375/500/1000 experiment, the“f” designation denotes the 393/500/1000 experiment, the “g” designationdenotes the 375/200/1000 experiment, while the “g′” designation denotesthe 393/200/1000 experiment.

From FIG. 32 it can be seen that the hydrocarbon liquids produced in the393° C. experiments, represented by the “a′-g′” bars of 272-283,generally contain more of the respective aromatic hydrocarbon compoundsas compared to the corresponding experiment completed at the samepressure and stress but at the lower 375° C. temperature, as representedby the “a-g” bars of 272-283. By comparing each respective neighboringpair of bars (e.g., a and a′, b and b′, etc.) for each correspondingpair of experiments differing only in temperature conditions it can alsobe seen that the effect of temperature is similar in magnitude, but morepronounced than the effect of stress and that the effect of temperatureand stress are both much more pronounced than the effect of pressure onaromatic hydrocarbon compound production. It is also noted that theeffect of increased pressure appears to partially retard the effect ofstress.

FIG. 33 is a bar graph of the weight ratio of the normal hydrocarboncompounds to like carbon number aromatic hydrocarbon compounds for eachof the seven 375° C. and seven 393° C. experimental data discussed inExamples 6-19 in the Experimental section herein. The compound weightratios were obtained through the experimental procedures, samplecollection and analytical techniques discussed above for FIG. 30 and inthe Experiments section. For clarity, the normal hydrocarbon compound toaromatic hydrocarbon compound weight ratios are derived as a ratio of aparticular normal hydrocarbon compound's peak area in one experiment toa particular aromatic hydrocarbon compound's peak area for the sameparticular experiment. Thus the graphed weight ratios represent a weightratio of two different compounds produced in the same experiment. They-axis 290 represents the weight ratio of two compounds for a givenexperiment. The x-axis 291 contains the identity of each depictedcompound ratio. The bars 292 a-g represent the weight ratio ofn-C6/benzene (n-C6/Bnz) at 375° C. while the bars 292 a′-g′ representthe weight ratio of n-C6/benzene at 393° C. It can be seen that the 76.4value of bar 292 a exceeds the y-axis scale of 60.0. The bars 293 a-grepresent the weight ratio of n-C7/toluene (n-C7/Tol) at 375° C. whilethe bars 293 a′-g′ represent the weight ratio of n-C7/toluene at 393° C.The bars 294 a-g represent the weight ratio of n-C8/ethylbenzene(n-C8/EB) at 375° C. while the bars 294 a′-g′ represent the weight ratioof n-C8/ethylbenzene at 393° C. The bars 295 a-g represent the weightratio of n-C8/ortho-xylene (n-C8/o-xyl) at 375° C. while the bars 295a′-g′ represent the weight ratio of n-C8/ortho-xylene at 393° C. Thebars 296 a-g represent the weight ratio of n-C8/meta-xylene (n-C8/m-xyl)at 375° C. while the bars 296 a′-g′ represent the weight ratio ofn-C8/meta-xylene at 393° C. The bars 297 a-g represent the weight ratioof n-C9/1-ethyl-3-methylbenzene (1E3M Bnz) at 375° C. while the bars 297a′-g′ represent the weight ratio of n-C9/1-ethyl-3-methylbenzene at 393°C. The bars 298 a-g represent the weight ratio ofn-C9/1-ethyl-4-methylbenzene (n-C9/1E4M Bnz) at 375° C. while the bars298 a′-g′ represent the weight ratio of n-C9/1-ethyl-4-methylbenzene at393° C. The bars 279 a-g represent the weight ratio ofn-C9/1,2,4-trimethylbenzene (n-C9/1,2,4TM Bnz) at 375° C. while the bars299 a′-g′ represent the weight ratio of n-C9/1,2,4-trimethylbenzene at393° C. The bars 300 a-g represent the weight ratio ofn-C10/1-ethyl-2,3-dimethylbenzene (n-C10/1E 2,3DM Bnz) at 375° C. whilethe bars 300 a′-g′ represent the weight ratio ofn-C10/1-ethyl-2,3-dimethylbenzene at 393° C. The bars 281 a-g representthe weight ratio of n-C10/tetralin at 375° C. while the bars 301 a′-g′represent the weight ratio of n-C10/tetralin at 393° C. The bars 302 a-grepresent the weight ratio of n-C12/2-methylnaphthalene (n-C12/2M Naph)at 375° C. while the bars 302 a′-g′ represent the weight ratio ofn-C12/2-methylnaphthalene at 393° C. The bars 303 a-g represent theweight ratio of n-C12/1-methylnaphthalene (n-C12/1M Naph) at 375° C.while the bars 303 a′-g′ represent the weight ratio ofn-C12/1-methylnaphthalene at 393° C. For each of the compound ratiogroups, the “a” designation denotes the 375/500/0 experiment, the “a′”designation denotes the 393/500/0 experiment, the “b” designationdenotes the 375/200/0 experiment, the “b′” designation denotes the393/200/0 experiment, the “c” designation denotes the 375/500/400experiment, the “c′” designation denotes the 393/500/400 experiment, the“d” designation denotes the 375/200/400 experiment, the “d′” designationdenotes the 393/200/400 experiment, the “e” designation denotes the375/50/400 experiment, the “e′” designation denotes the 393/50/400experiment, the “f” designation denotes the 375/500/1000 experiment, the“f” designation denotes the 393/500/1000 experiment, the “g” designationdenotes the 375/200/1000 experiment, while the “g′” designation denotesthe 393/200/1000 experiment.

From FIG. 33 it can be seen that the graphed bars have been generallyordered consecutively from highest ratio value to lowest ratio value.For each of the compound ratio groups, ratio bars are in the followingorder: the “a” designation denoting the 375/500/0 experiment, the “b”designation denoting the 375/200/0 experiment, the “c” designationdenoting the 375/500/400 experiment, the “d” designation denoting the375/200/400 experiment, the “e” designation denoting the 375/50/400experiment, the “f” designation denoting the 375/500/1000 experiment,the “g” designation denoting the 375/200/1000 experiment, the “a′”designation denoting the 393/500/0 experiment, the “V” designationdenoting the 393/200/0 experiment, the “c′” designation denoting the393/500/400 experiment, the “d′” designation denoting the 393/200/400experiment, the “e′” designation denoting the 393/50/400 experiment, the“f” designation denoting the 393/500/1000 experiment, and the “g′”designation denotes the 393/200/1000 experiment. Thus the orderingincludes the temperature difference having the greatest effect on thecompositional change with the stress differences having the secondlargest effect on the compositional change. Further, the pressuredifference has the smallest effect on composition and its effect isopposite to both temperature and stress.

FIG. 34 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number cyclic hydrocarbon compounds for each ofthe seven 393° C. experimental data discussed in Examples 13-19 in theExperimental section herein. The compound weight ratios were obtainedthrough the experimental procedures, sample collection and analyticaltechniques discussed above for FIG. 30 and in the Experiments section.For clarity, the normal hydrocarbon compound to cyclic hydrocarboncompound weight ratios are derived as a ratio of a particular normalhydrocarbon compound's peak area in one experiment to a particularcyclic hydrocarbon compound's peak area for the same particularexperiment. Thus the graphed weight ratios represent a weight ratio oftwo different compounds produced in the same experiment. The y-axis 310represents the weight ratio of two compounds for a given experiment. Thex-axis 311 contains the identity of each depicted compound ratio. Thebars 312 a-g represent the weight ratio of n-C7 to cis 1,3-dimethylcyclopentane (n-C7/c1-3DM CyC5). The bars 313 a-g represent the weightratio of n-C7 to trans 1,3-dimethyl cyclopentane (n-C7/t1-3DM CyC5). Thebars 314 a-g represent the weight ratio of n-C7 to trans 1,2-dimethylcyclopentane (n-C7/t1-2DM CyC5). The bars 315 a-g represent the weightratio of n-C7 to methyl cyclohexane (n-C7/M CyC6). The bars 316 a-grepresent the weight ratio of n-C7 to ethyl cyclopentane (n-C7/E CyC5).The bars 317 a-g represent the weight ratio of n-C8 to 1,1-dimethylcyclohexane (n-C8/1-1DM CyC6). The bars 318 a-g represent the weightratio of n-C8 to trans 1,2-dimethyl cyclohexane (n-C8/t1-2DM CyC6). Thebars 319 a-g represent the weight ratio of n-C8 to ethyl cyclohexane(n-C8/E CyC6). For each of the compound ratio groups, the “a”designation denotes the 393/500/0 experiment, the “b” designationdenotes the 393/200/0 experiment, the “c” designation denotes the393/500/400 experiment, the “d” designation denotes the 393/200/400experiment, the “e” designation denotes the 393/50/400 experiment, the“f” designation denotes the 393/500/1000 experiment, while the “g”designation denotes the 393/200/1000 experiment.

From FIG. 34 it can be seen that the hydrocarbon liquids produced in thetwo 1,000 psi stressed experiments, represented by the “f” and “g” barsof 312-319, generally contain the most respective cyclic hydrocarboncompounds relative to the respective corresponding same carbon numbernormal hydrocarbon compound. It also can be seen that for the two 1,000psi stress experiments, the lower initial argon pressure (200 psigargon) experiment represented by the “g” bars is generally more enrichedin cyclic compounds relative to the higher initial argon pressure (500psig argon) experiment represented by the “f” bars. From FIG. 34 it canalso be seen that the hydrocarbon liquids produced in the three 400 psistressed experiments, represented by the “c”, “d” and “f” bars,generally contain an increased amount of cyclic hydrocarbon compoundsrelative to the unstressed experiments (i.e., bars “a” and “b”) but alower amount of cyclic hydrocarbon compounds relative to the 1,000 psistressed experiments (bars “f” and “g”). It also can be seen that forthe three 400 psi stress experiments, the lowest initial argon pressure(50 psig argon) experiment represented by the “e” bars is generally moreenriched in cyclic compounds relative to the middle initial argonpressures (200 psig argon) experiment represented by the “d” bars andthe highest initial argon pressures (500 psigg argon) experimentrepresented by the “c” bars, with the middle initial argon pressures(200 psig argon) experiment represented the “d” bars generally fallingbetween the highest and lowest initial argon pressure experiments. Bycomparing the effect of the 0, 400, and 1,000 psi stressed data atconsistent initial argon pressures (i.e., the a, c, and f data all at500 psig initial argon or the b, d, and g data all at 200 psig initialargon) to the three 400 psi stress at different initial argon pressuresdata (i.e., the c, d, and e data), it becomes apparent that thecompositional changes due to step changes in stress (i.e., 0 psi to 400psi and 400 psi to 1,000 psi) are much more pronounced than thecompositional changes due to step changes in pressure (i.e., 50 psig to200 psig and 200 psig to 500 psig). It is also noted that the effect ofincreased pressure appears to partially retard the effect of increasedstress. Thus pyrolyzing oil shale under increasing levels of stressappears to enrich the produced hydrocarbon liquid in cyclic compoundswhile decreasing pressure appears to enhance cyclic compound production.Further, the magnitude of compositional changed due to changes in stressappears to be more significant than the magnitude of the compositionalchange due to changes in pressure.

FIG. 35 is a bar graph of the weight ratio of the normal hydrocarboncompounds to like carbon number cyclic hydrocarbon compounds for each ofthe seven 375° C. and seven 393° C. experimental data discussed inExamples 6-19 in the Experimental section herein. The compound weightratios were obtained through the experimental procedures, samplecollection and analytical techniques discussed above for FIG. 30 and inthe Experiments section. For clarity, the normal hydrocarbon compound tocyclic hydrocarbon compound weight ratios are derived as a ratio of aparticular normal hydrocarbon compound's peak area in one experiment toa particular cyclic hydrocarbon compound's peak area for the sameparticular experiment. Thus the graphed weight ratios represent a weightratio of two different compounds produced in the same experiment. They-axis 330 represents the weight ratio of two compounds for a givenexperiment. The x-axis 331 contains the identity of each depictedcompound ratio. The bars 332 a-g represent the weight ratio of n-C7 tocis 1,3-dimethyl cyclopentane (n-C7/c1-3DM CyC5) at 375° C. while thebars 332 a′-g′ represent the weight ratio of n-C7 to cis 1,3-dimethylcyclopentane at 393° C. The bars 333 a-g represent the weight ratio oftrans 1,3-dimethyl cyclopentane (n-C7/t1-3DM CyC5) at 375° C. while thebars 333 a′-g′ represent the weight ratio of trans 1,3-dimethylcyclopentane at 393° C. The bars 334 a-g represent the weight ratio ofn-C7 to trans 1,2-dimethyl cyclopentane (n-C7/t1-2DM CyC5) at 375° C.while the bars 334 a′-g′ represent the weight ratio of n-C7 to trans1,2-dimethyl cyclopentane at 393° C. The bars 335 a-g represent theweight ratio of n-C7 to methyl cyclohexane (n-C7/M CyC6) at 375° C.while the bars 335 a′-g′ represent the weight ratio of n-C7 to methylcyclohexane at 393° C. The bars 336 a-g represent the weight ratio ofn-C7 to ethyl cyclopentane (n-C7/E CyC5) at 375° C. while the bars 336a′-g′ represent the weight ratio of n-C7 to ethyl cyclopentane at 393°C. The bars 337 a-g represent the weight ratio of n-C8 to 1,1-dimethylcyclohexane (n-C8/1-1DM CyC6) at 375° C. while the bars 337 a′-g′represent the weight ratio of n-C8 to 1,1-dimethyl cyclohexane at 393°C. The bars 338 a-g represent the weight ratio of n-C8 to trans1,2-dimethyl cyclohexane (n-C8/t1-2DM CyC6) at 375° C. while the bars338 a′-g′ represent the weight ratio of n-C8 to trans 1,2-dimethylcyclohexane at 393° C. The bars 339 a-g represent the weight ratio ofn-C8 to ethyl cyclohexane (n-C8/E CyC6) at 375° C. while the bars 339a′-g′ represent the weight ratio of n-C8 to ethyl cyclohexane at 393° C.For each of the compound ratio groups, the “a” designation denotes the375/500/0 experiment, the “a′” designation denotes the 393/500/0experiment, the “b” designation denotes the 375/200/0 experiment, the“b′” designation denotes the 393/200/0 experiment, the “c” designationdenotes the 375/500/400 experiment, the “c′” designation denotes the393/500/400 experiment, the “d” designation denotes the 375/200/400experiment, the “d′” designation denotes the 393/200/400 experiment, the“e” designation denotes the 375/50/400 experiment, the “e′” designationdenotes the 393/50/400 experiment, the “f” designation denotes the375/500/1000 experiment, the “f” designation denotes the 393/500/1000experiment, the “g” designation denotes the 375/200/1000 experiment,while the “g′” designation denotes the 393/200/1000 experiment.

From FIG. 35 it can be seen that the graphed bars have been generallyordered consecutively from highest ratio value to lowest ratio value.For each of the compound ratio groups, ratio bars are in the followingorder: the “a” designation denoting the 375/500/0 experiment, the “b”designation denoting the 375/200/0 experiment, the “c” designationdenoting the 375/500/400 experiment, the “d” designation denoting the375/200/400 experiment, the “e” designation denoting the 375/50/400experiment, the “f” designation denoting the 375/500/1000 experiment,the “g” designation denoting the 375/200/1000 experiment, the “a′”designation denoting the 393/500/0 experiment, the “V” designationdenoting the 393/200/0 experiment, the “c′” designation denoting the393/500/400 experiment, the “d′” designation denoting the 393/200/400experiment, the “e′” designation denoting the 393/50/400 experiment, the“f” designation denoting the 393/500/1000 experiment, and the “g′”designation denotes the 393/200/1000 experiment. From FIG. 34 it can beseen that the hydrocarbon liquids produced in the 393° C. experiments,represented by the “a′-g′” bars of 332-339, generally contain more ofthe respective cyclic hydrocarbon compounds as compared to thecorresponding experiment completed at the same pressure and stress butat the lower 375° C. temperature, as represented by the “a-g” bars of332-339. By comparing each respective pair of bars (e.g., a and a′, band b′, etc.) for each corresponding pair of experiments differing onlyin temperature conditions it can also be seen that the effect oftemperature is similar in magnitude, but more pronounced than the effectof stress and that the effect of temperature and stress are both muchmore pronounced than the effect of pressure on cyclic hydrocarboncompound production. It is also noted that the effect of increasedpressure appears to partially retard the effect of stress. Thus theordering in FIG. 35 includes the temperature difference having thegreatest effect on the compositional change with the stress differenceshaving the second largest effect on the compositional change. Further,the pressure difference has the smallest effect on composition and itseffect is opposite to both temperature and stress.

FIG. 36 is a bar graph of the weight ratio of several normal hydrocarboncompounds to like carbon number isoprenoid hydrocarbon compounds foreach of the seven 393° C. experimental data discussed in Examples 13-19in the Experimental section herein. The compound weight ratios wereobtained through the experimental procedures, sample collection andanalytical techniques discussed above for FIG. 30 and in the Experimentssection. For clarity, the normal hydrocarbon compound to isoprenoidhydrocarbon compound weight ratios are derived as a ratio of aparticular normal hydrocarbon compound's peak area in one experiment toa particular isoprenoid hydrocarbon compound's peak area for the sameparticular experiment. Thus the graphed weight ratios represent a weightratio of two different compounds produced in the same experiment. They-axis 350 represents the weight ratio of two compounds for a givenexperiment. The x-axis 351 contains the identity of each depictedcompound ratio. The bars 352 a-g represent the weight ratio of n-C9 toIP-9. The bars 353 a-g represent the weight ratio of n-C10 to IP-10. Thebars 354 a-g represent the weight ratio of n-C11 to IP-11. The bars 355a-g represent the weight ratio of n-C13 to IP-13. The bars 356 a-grepresent the weight ratio of n-C14 to IP-14. The bars 357 a-g representthe weight ratio of n-C15 to IP-15. The bars 358 a-g represent theweight ratio of n-C16 to IP-16. The bars 359 a-g represent the weightratio of n-C18 to IP-18. The bars 360 a-g represent the weight ratio ofn-C19 to pristane. For each of the compound ratio groups, the “a”designation denotes the 393/500/0 experiment, the “b” designationdenotes the 393/200/0 experiment, the “c” designation denotes the393/500/400 experiment, the “d” designation denotes the 393/200/400experiment, the “e” designation denotes the 393/50/400 experiment, the“f” designation denotes the 393/500/1000 experiment, while the “g”designation denotes the 393/200/1000 experiment.

From FIG. 36 it can be seen that the hydrocarbon liquids produced in thetwo 1,000 psi stressed experiments, represented by the “f” and “g” barsof 312-319, generally contain the least respective isoprenoidhydrocarbon compounds relative to the respective corresponding samecarbon number normal hydrocarbon compound. It is however noted that forthe IP-15, IP-18 and IP19 ratios, the 393/200/1000 data of therespective “g” experiment is lower than the 393/50/400 data of therespective “e” experiment. It also can be seen that for the two 1,000psi stress experiments, the lower initial argon pressure (200 psigargon) experiment represented by the “g” bars is generally more depletedof isoprenoid compounds relative to the higher initial argon pressure(500 psig argon) experiment represented by the “f” bars. It is howeveragain noted that for the IP-15, IP-18 and IP19 ratios, the 393/200/1000data of the respective “g” experiment is lower than the 393/500/1000data of the respective “f” experiment. From FIG. 36 it can also be seenthat the hydrocarbon liquids produced in the three 400 psi stressedexperiments, represented by the “c”, “d” and “f” bars, generally containa decreased amount of isoprenoid hydrocarbon compounds relative to theunstressed experiments (i.e., bars “a” and “b”) but a greater amount ofisoprenoid hydrocarbon compounds relative to the 1,000 psi stressedexperiments (bars “f” and “g”). It also can be seen that for the three400 psi stress experiments, the lowest initial argon pressure (50 psigargon) experiment represented by the “e” bars is generally more depletedof isoprenoid compounds relative to the middle initial argon pressures(200 psig argon) experiment represented by the “d” bars and the highestinitial argon pressures (500 psig argon) experiment represented by the“c” bars, with the middle initial argon pressures (200 psig argon)experiment represented the “d” bars generally falling between thehighest and lowest initial argon pressure experiments. By comparing theeffect of the 0, 400, and 1,000 psi stressed data at consistent initialargon pressures (i.e., the a, c, and f data all at 500 psig initialargon or the b, d, and g data all at 200 psig initial argon) to thethree 400 psi stress at different initial argon pressures data (i.e.,the c, d, and e data), it becomes apparent that the compositionalchanges due to step changes in stress (i.e., 0 psi to 400 psi and 400psi to 1,000 psi) are of a similar magnitude to the compositionalchanges due to step changes in pressure (i.e., 50 psig to 200 psig and200 psig to 500 psig). It is also noted that the effect of increasedpressure appears to partially retard the effect of increased stress.Thus pyrolyzing oil shale under increasing levels of stress appears todeplete the produced hydrocarbon liquid in isoprenoid compounds whiledecreasing pressure appears to deplete isoprenoid compound production.Further, the magnitude of compositional changed due to changes in stressappears to be of similar magnitude to the magnitude of the compositionalchange due to changes in pressure.

FIG. 37 is a bar graph of the weight ratio of the normal hydrocarboncompounds to like carbon number isoprenoid hydrocarbon compounds foreach of the seven 375° C. and seven 393° C. experimental data discussedin Examples 6-19 in the Experimental section herein. The compound weightratios were obtained through the experimental procedures, samplecollection and analytical techniques discussed above for FIG. 30 and inthe Experiments section. For clarity, the normal hydrocarbon compound toisoprenoid hydrocarbon compound weight ratios are derived as a ratio ofa particular normal hydrocarbon compound's peak area in one experimentto a particular isoprenoid hydrocarbon compound's peak area for the sameparticular experiment. Thus the graphed weight ratios represent a weightratio of two different compounds produced in the same experiment. They-axis 370 represents the weight ratio of two compounds for a givenexperiment. The x-axis 371 contains the identity of each depictedcompound ratio. The bars 372 a-g′ represent the weight ratio of n-C9 toIP-9. The bars 373 a-g′ represent the weight ratio of n-C10 to IP-10.The bars 374 a-g′ represent the weight ratio of n-C11 to IP-11. The bars375 a-g′ represent the weight ratio of n-C13 to IP-13. The bars 376 a-g′represent the weight ratio of n-C14 to IP-14. The bars 377 a-g′represent the weight ratio of n-C15 to IP-15. The bars 378 a-g′represent the weight ratio of n-C16 to IP-16. The bars 379 a-g′represent the weight ratio of n-C18 to IP-18. The bars 380 a-g′represent the weight ratio of n-C19 to pristane. For each of thecompound ratio groups, the “a” designation denotes the 375/500/0experiment, the “a′” designation denotes the 393/500/0 experiment, the“b” designation denotes the 375/200/0 experiment, the “b′” designationdenotes the 393/200/0 experiment, the “c” designation denotes the375/500/400 experiment, the “c′” designation denotes the 393/500/400experiment, the “d” designation denotes the 375/200/400 experiment, the“d′” designation denotes the 393/200/400 experiment, the “e” designationdenotes the 375/50/400 experiment, the “e′” designation denotes the393/50/400 experiment, the “f” designation denotes the 375/500/1000experiment, the “f” designation denotes the 393/500/1000 experiment, the“g” designation denotes the 375/200/1000 experiment, while the “g′”designation denotes the 393/200/1000 experiment.

From FIG. 37 it can be seen that the graphed bars have been generallyordered consecutively from lowest ratio value to highest ratio value.For each of the compound ratio groups, ratio bars are in the followingorder: the “a” designation denoting the 375/500/0 experiment, the “b”designation denoting the 375/200/0 experiment, the “c” designationdenoting the 375/500/400 experiment, the “d” designation denoting the375/200/400 experiment, the “e” designation denoting the 375/50/400experiment, the “f” designation denoting the 375/500/1000 experiment,the “g” designation denoting the 375/200/1000 experiment, the “a′”designation denoting the 393/500/0 experiment, the “b′” designationdenoting the 393/200/0 experiment, the “c′” designation denoting the393/500/400 experiment, the “d′” designation denoting the 393/200/400experiment, the “e′” designation denoting the 393/50/400 experiment, the“f” designation denoting the 393/500/1000 experiment, and the “g′”designation denotes the 393/200/1000 experiment. From FIG. 37 it can beseen that the hydrocarbon liquids produced in the 393° C. experiments,represented by the “a′-g′” bars of 372-380, generally contain less ofthe respective isoprenoid hydrocarbon compounds as compared to thecorresponding experiment completed at the same pressure and stress butat the lower 375° C. temperature, as represented by the “a-g” bars of372-380. By comparing each respective pair of bars (e.g., a and a′, band b′, etc.) for each corresponding pair of experiments differing onlyin temperature conditions it can also be seen that the effect oftemperature is more pronounced than the effect of stress and morepronounced than the effect of pressure on isoprenoid hydrocarboncompound production. It is also noted that the effect of increasedpressure appears to partially retard the effect of stress. Thus theordering in FIG. 37 includes the temperature difference having thegreatest effect on the compositional change with the stress differenceshaving a reduced, but second largest effect on the compositional change.Further, the pressure difference has the smallest effect on compositionand its effect is opposite to the effect of both temperature and stress.

FIG. 38 is a bar graph of the weight ratio of the certain hydrocarboncompounds to similar carbon number isoprenoid hydrocarbon compounds foreach of the seven 375° C. and seven 393° C. experimental data discussedin Examples 6-19 in the Experimental section herein. The compound weightratios were obtained through the experimental procedures, samplecollection and analytical techniques discussed above for FIG. 30 and inthe Experiments section. For clarity, the hydrocarbon compound toisoprenoid hydrocarbon compound weight ratios are derived as a ratio ofa particular hydrocarbon compound's peak area in one experiment to aparticular isoprenoid hydrocarbon compound's peak area for the sameparticular experiment. Thus the graphed weight ratios represent a weightratio of two different compounds produced in the same experiment. They-axis 390 represents the weight ratio of two compounds for a givenexperiment. The x-axis 391 contains the identity of each depictedcompound ratio. The bars 392 a-g′ represent the weight ratio of1-ethyl-3,5-dimethylbenzene (1E3-5DM Bnz) to IP-10. The bars 393 a-g′represent the weight ratio of 1-ethyl-3,5-dimethylbenzene to IP-11. Thebars 394 a-g′ represent the weight ratio of 3-methyldodecane (3MC-12) toIP-13. The bars 395 a-g′ represent the weight ratio of 3-methyldodecaneto IP-14. The bars 396 a-g′ represent the weight ratio of3-methyldodecane to IP-15. The bars 397 a-g′ represent the weight ratioof 3-methyldodecane to IP-16. The bars 398 a-g′ represent the weightratio of 3-methyldodecane to IP-18. The bars 399 a-g′ represent theweight ratio of 3-methyldodecane to pristane. For each of the compoundratio groups, the “a” designation denotes the 375/500/0 experiment, the“a′” designation denotes the 393/500/0 experiment, the “b” designationdenotes the 375/200/0 experiment, the “b′” designation denotes the393/200/0 experiment, the “c” designation denotes the 375/500/400experiment, the “c′” designation denotes the 393/500/400 experiment, the“d” designation denotes the 375/200/400 experiment, the “d′” designationdenotes the 393/200/400 experiment, the “e” designation denotes the375/50/400 experiment, the “e′” designation denotes the 393/50/400experiment, the “f” designation denotes the 375/500/1000 experiment, the“f” designation denotes the 393/500/1000 experiment, the “g” designationdenotes the 375/200/1000 experiment, while the “g′” designation denotesthe 393/200/1000 experiment.

FIG. 38 was developed to provide an alternate comparison of the changesin isoprenoid production from changes in experimental conditions. FIGS.36 & 37 compare isoprenoid production to like carbon number normalhydrocarbon compounds. However, from FIG. 29 it is apparent that normalhydrocarbon compound production is reduced by increasing stress,increasing temperature and decreasing pressure, just as isoprenoidhydrocarbon compound production is reduced by increasing stress,increasing temperature and decreasing pressure. Thus the ratiocomparisons depicted in FIGS. 36 & 37 actually compare the reduction innormal hydrocarbon compound production relative to the reduction inisoprenoid hydrocarbon production, which both decrease with increasingstress, increasing temperature, and decreasing pressure. FIG. 38provides an alternate comparison to better gauge the effect of stress,temperature and pressure changes on isoprenoid production. FIG. 38provides a ratio of selective isoprenoid hydrocarbon compounds to either1-ethyl-3,5-dimethylbenzene (1E3-5DM Bnz) or 3-methyldodecane (3MC-12).These two compounds were chosen for comparison because they are of asimilar elution time to the respective isoprenoid compounds used in aparticular ratio and have a fairly consistent concentration over theentire stress, temperature and pressure ranges tested in all theexperiments, which can be seen by looking at the weight ratioconcentration plots in FIG. 29 for each of 1-ethyl-3,5-dimethylbenzene(1E3-5DMBz) or 3-methyldodecane (3MC12).

From FIG. 38 it can be seen that the graphed bars have been generallyordered consecutively from lowest ratio value to highest ratio value.For each of the compound ratio groups, ratio bars are in the followingorder: the “a” designation denoting the 375/500/0 experiment, the “b”designation denoting the 375/200/0 experiment, the “c” designationdenoting the 375/500/400 experiment, the “d” designation denoting the375/200/400 experiment, the “e” designation denoting the 375/50/400experiment, the “f” designation denoting the 375/500/1000 experiment,the “g” designation denoting the 375/200/1000 experiment, the “a′”designation denoting the 393/500/0 experiment, the “V” designationdenoting the 393/200/0 experiment, the “c′” designation denoting the393/500/400 experiment, the “d′” designation denoting the 393/200/400experiment, the “e′” designation denoting the 393/50/400 experiment, the“f” designation denoting the 393/500/1000 experiment, and the “g′”designation denotes the 393/200/1000 experiment. From FIG. 38 it can beseen that the hydrocarbon liquids produced in the 393° C. experiments,represented by the “a′-g′” bars of 372-380, generally contain less ofthe respective isoprenoid hydrocarbon compounds as compared to thecorresponding experiment completed at the same pressure and stress butat the lower 375° C. temperature, as represented by the “a-g” bars of372-380. By comparing each respective pair of bars (e.g., a and a′, band b′, etc.) for each corresponding pair of experiments differing onlyin temperature conditions it can also be seen that the effect oftemperature is more pronounced than the effect of stress and morepronounced than the effect of pressure on isoprenoid hydrocarboncompound production. It is also noted that the effect of increasedpressure appears to partially retard the effect of stress. Thus theordering in FIG. 38 includes the temperature difference having thegreatest effect on the compositional change with the stress differenceshaving a reduced, but second largest effect on the compositional change.Further, the pressure difference has the smallest effect on compositionand its effect is opposite to the effect of both temperature and stress.

From the above-described data discussed in FIGS. 29-38, it can be seenthat temperature, pressure and lithostatic stress can affect thecomposition of produced fluids generated within an organic-rich rock viaheating and pyrolysis. This implies that the composition of the producedhydrocarbon fluid from in situ heating and pyrolysis processes can alsobe influenced by selecting, maintaining or in some cases controlling oneor more of in situ temperature, in situ pressure, and in situlithostatic stress conditions of the organic-rich rock formation beingheated in the in situ process. By selecting, maintaining, or in somecases controlling the heating and pyrolysis conditions of oil shale, acondensable hydrocarbon fluid product that has desired compositionalproperties may be obtained. Such a product may be suitable for refininginto gasoline and distillate products. Further, such a product, eitherbefore or after further fractionation, may have utility as a feed stockfor certain chemical processes.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have one or more of a n-C6 to benzene weightratio less than 35.0, a n-C7 to toluene weight ratio less than 7.0, an-C8 to ethylbenzene weight ratio less than 16.0, a n-C8 to ortho-xyleneweight ratio less than 7.0, a n-C8 to meta-xylene weight ratio less than1.9, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 8.2, an-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.4, a n-C9 to1,2,4-trimethylbenzene weight ratio less than 2.7, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, a n-C10 totetralin weight ratio less than 25.0, a n-C12 to 2-methylnaphthaleneweight ratio less than 4.9, and a n-C12 to 1-methylnaphthalene weightratio less than 6.9. In some embodiments the condensable hydrocarbonportion may have two or more, three or more or four or more of theweight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion has a n-C6 tobenzene weight ratio less than 35.0, less than 25, 15, 10 or 7. In someembodiments the condensable hydrocarbon portion has a n-C7 to tolueneweight ratio less than 7.0, less than 6, 5, 4 or 3. In some embodimentsthe condensable hydrocarbon portion has a n-C8 to ethylbenzene weightratio less than 16.0, less than 13, 10, 5 or 2. In some embodiments thecondensable hydrocarbon portion has a n-C8 to ortho-xylene weight ratioless than 7.0, less than 6, 5, 4 or 2. In some embodiments thecondensable hydrocarbon portion has a n-C8 to meta-xylene weight ratioless than 1.9, less than 1.8, 1.7, 1.6 or 1.5. In some embodiments thecondensable hydrocarbon portion has a n-C9 to 1-ethyl-3-methylbenzeneweight ratio less than 8.2, less than 7, 6, 4 or 2. In some embodimentsthe condensable hydrocarbon portion has a n-C9 to1-ethyl-4-methylbenzene weight ratio less than 4.4, less than 4.0, 3.5,3.0 or 2.0. In some embodiments the condensable hydrocarbon portion hasa n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.7, less than2.5, 2.0, 1.5 or 1.0. In some embodiments the condensable hydrocarbonportion has a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio lessthan 13.5, less than 12, 10, 7 or 5. In some embodiments the condensablehydrocarbon portion has a n-C10 to tetralin weight ratio less than 25.0,less than 20, 15, or 10. In some embodiments the condensable hydrocarbonportion has a n-C12 to 2-methylnaphthalene weight ratio less than 4.9,less than 4.5, 4.0, 3.5 or 3. In some embodiments the condensablehydrocarbon portion has a n-C12 to 1-methylnaphthalene weight ratio lessthan 6.9, 6.0, 4.0, 3.0, or 2.5.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C6 to benzene weight ratio less than 24.0, a n-C7 to tolueneweight ratio less than 6.6, a n-C8 to ethylbenzene weight ratio lessthan 15.0, a n-C8 to ortho-xylene weight ratio less than 6.6, a n-C8 tometa-xylene weight ratio less than 1.8, a n-C9 to1-ethyl-3-methylbenzene weight ratio less than 7.9, a n-C9 to1-ethyl-4-methylbenzene weight ratio less than 4.3, a n-C9 to1,2,4-trimethylbenzene weight ratio less than 2.6, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 13.1, a n-C10 totetralin weight ratio less than 23.7, a n-C12 to 2-methylnaphthaleneweight ratio less than 5.0, and a n-C12 to 1-methylnaphthalene weightratio less than 6.8. In some embodiments the condensable hydrocarbonportion may have two or more, three or more or four or more of theweight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C6 to benzene weight ratio less than 13.4, a n-C7 to tolueneweight ratio less than 5.1, a n-C8 to ethylbenzene weight ratio lessthan 12.3, a n-C8 to ortho-xylene weight ratio less than 5.3, a n-C8 tometa-xylene weight ratio less than 1.5, a n-C9 to1-ethyl-3-methylbenzene weight ratio less than 5.9, a n-C9 to1-ethyl-4-methylbenzene weight ratio less than 3.8, a n-C9 to1,2,4-trimethylbenzene weight ratio less than 2.2, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 12.2, a n-C10 totetralin weight ratio less than 23.4, a n-C12 to 2-methylnaphthaleneweight ratio less than 4.0, and a n-C12 to 1-methylnaphthalene weightratio less than 6.1. In some embodiments the condensable hydrocarbonportion may have two or more, three or more or four or more of theweight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than13.1, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than14.9, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than7.0, a n-C7 to methyl cyclohexane weight ratio less than 5.2, a n-C7 toethyl cyclopentane weight ratio less than 11.3, a n-C8 to 1,1-dimethylcyclohexane weight ratio less than 16.0, a n-C8 to trans 1,2-dimethylcyclohexane weight ratio less than 17.5, and a n-C8 to ethyl cyclohexaneweight ratio less than 12.3. In some embodiments the condensablehydrocarbon portion may have two or more, three or more or four or moreof the weight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than12.7, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than14.7, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than6.6, a n-C7 to methyl cyclohexane weight ratio less than 5.0, a n-C7 toethyl cyclopentane weight ratio less than 10.9, a n-C8 to 1,1-dimethylcyclohexane weight ratio less than 15.4, a n-C8 to trans 1,2-dimethylcyclohexane weight ratio less than 16.5, and a n-C8 to ethyl cyclohexaneweight ratio less than 12.0. In some embodiments the condensablehydrocarbon portion may have two or more, three or more or four or moreof the weight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than10.3, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than11.6, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than5.9, a n-C7 to methyl cyclohexane weight ratio less than 4.1, a n-C7 toethyl cyclopentane weight ratio less than 9.5, a n-C8 to 1,1-dimethylcyclohexane weight ratio less than 13.9, a n-C8 to trans 1,2-dimethylcyclohexane weight ratio less than 12.3, and a n-C8 to ethyl cyclohexaneweight ratio less than 10.3. In some embodiments the condensablehydrocarbon portion may have two or more, three or more or four or moreof the weight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion has a n-C7 tocis 1,3-dimethyl cyclopentane weight ratio less than 13.1, 12, 10, 7, or5. In some embodiments the condensable hydrocarbon portion has a n-C7 totrans 1,3-dimethyl cyclopentane weight ratio less than 14.9, 13, 10, 7or 5. In some embodiments the condensable hydrocarbon portion has a n-C7to trans 1,2-dimethyl cyclopentane weight ratio less than 7.0, 6.0, 5.0or 4.0. In some embodiments the condensable hydrocarbon portion has an-C7 to methyl cyclohexane weight ratio less than 5.2, 4.7, 4.2, 3.5 or2.0. In some embodiments the condensable hydrocarbon portion has a n-C7to ethyl cyclopentane weight ratio less than 11.3, 10.0, 8.0, 6.5 or5.0. In some embodiments the condensable hydrocarbon portion has a n-C8to 1,1-dimethyl cyclohexane weight ratio less than 15.4, 14.0, 12.0,10.0 or 9.0. In some embodiments the condensable hydrocarbon portion hasa n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 16.5,15.0, 12.0, 9.0 or 6.0. In some embodiments the condensable hydrocarbonportion has a n-C8 to ethyl cyclohexane weight ratio less than 12.0,10.0, 8.0, 6.0 or 5.0.

In some embodiments the condensable hydrocarbon portion has a n-C7 tocis 1,3-dimethyl cyclopentane weight ratio greater than 0.5 or 1.0, an-C7 to trans 1,3-dimethyl cyclopentane weight ratio greater than 0.5 or1.0, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio greater than0.5 or 1.0, a n-C7 to methyl cyclohexane weight ratio greater than 0.2or 0.5, a n-C7 to ethyl cyclopentane weight ratio greater than 0.5 or1.0, a n-C8 to 1,1-dimethyl cyclohexane weight ratio greater than 0.5 or1.0, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio greater than0.5 or 1.0, and/or a n-C8 to ethyl cyclohexane weight ratio greater than0.5 or 1.0.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C9 to IP-9 weight ratio greater than 2.4, a n-C10 to IP-10weight ratio greater than 1.4, a n-C11 to IP-11 weight ratio greaterthan 1.0, a n-C13 to IP-13 weight ratio greater than 1.1, a n-C14 toIP-14 weight ratio greater than 1.1, a n-C15 to IP-15 weight ratiogreater than 1.0, a n-C16 to IP-16 weight ratio greater than 0.8, an-C18 to IP-18 weight ratio greater than 1.0, and a n-C19 to pristaneweight ratio greater than 1.6. In some embodiments the condensablehydrocarbon portion may have two or more, three or more or four or moreof the weight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C9 to IP-9 weight ratio greater than 2.5, a n-C10 to IP-10weight ratio greater than 1.5, a n-C11 to IP-11 weight ratio greaterthan 1.1, a n-C13 to IP-13 weight ratio greater than 1.2, a n-C14 toIP-14 weight ratio greater than 1.2, a n-C15 to IP-15 weight ratiogreater than 1.1, a n-C16 to IP-16 weight ratio greater than 0.9, an-C18 to IP-18 weight ratio greater than 1.1, and a n-C19 to pristaneweight ratio greater than 1.8. In some embodiments the condensablehydrocarbon portion may have two or more, three or more or four or moreof the weight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a n-C9 to IP-9 weight ratio greater than 2.6, a n-C10 to IP-10weight ratio greater than 1.6, a n-C11 to IP-11 weight ratio greaterthan 1.2, a n-C13 to IP-13 weight ratio greater than 1.3, a n-C14 toIP-14 weight ratio greater than 1.4, a n-C15 to IP-15 weight ratiogreater than 1.4, a n-C16 to IP-16 weight ratio greater than 1.2, an-C18 to IP-18 weight ratio greater than 1.5, and a n-C19 to pristaneweight ratio greater than 2.4. In some embodiments the condensablehydrocarbon portion may have two or more, three or more or four or moreof the weight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion has a n-C9 toIP-9 weight ratio greater than 2.4, 3.0, 4.0, 5.0 or 6.0. In someembodiments the condensable hydrocarbon portion has a n-C10 to IP-10weight ratio greater than 1.4, 2.0, 2.5, 3.0 or 4.0. In some embodimentsthe condensable hydrocarbon portion has a n-C11 to IP-11 weight ratiogreater than 1.0, 1.5, 2.0, 2.5 or 3.5. In some embodiments thecondensable hydrocarbon portion has a n-C13 to IP-13 weight ratiogreater than 1.1, 1.5, 2.0, 2.5 or 3.0. In some embodiments thecondensable hydrocarbon portion has a n-C14 to IP-14 weight ratiogreater than 1.1, 2.0, 3.0, 4.0 or 5.0. In some embodiments thecondensable hydrocarbon portion has a n-C15 to IP-15 weight ratiogreater than 1.0, 1.5, 2.0, 3.0 or 4.0. In some embodiments thecondensable hydrocarbon portion has a n-C16 to IP-16 weight ratiogreater than 0.8, 1.0, 1.5, 2.0, 3.0 or 7.0. In some embodiments thecondensable hydrocarbon portion has a n-C18 to IP-18 weight ratiogreater than 1.0, 1.5, 2.0, 2.5 or 5.0. In some embodiments thecondensable hydrocarbon portion has a n-C19 to pristane weight ratiogreater than 2.4, 3.0, 3.5, 4.0 or 6.0.

In some embodiments the condensable hydrocarbon portion has a n-C9 toIP-9 weight ratio less than 15.0 or 10.0, a n-C10 to IP-10 weight ratioless than 15.0 or 10.0, a n-C11 to IP-11 weight ratio less than 15.0 or10.0, a n-C13 to IP-13 weight ratio less than 15.0 or 10.0, a n-C14 toIP-14 weight ratio less than 15.0 or 10.0, a n-C15 to IP-15 weight ratioless than 15.0 or 10.0, a n-C16 to IP-16 weight ratio less than 15.0 or10.0, a n-C18 to IP-18 weight ratio less than 15.0 or 10.0, and/or an-C19 to pristane weight ratio less than 15.0 or 10.0.

In some embodiments the condensable hydrocarbon portion may have one ormore of a ethyl-3,5-dimethylbenzene to IP-10 weight ratio greater than0.3, a 1 ethyl-3,5-dimethylbenzene to IP-11 weight ratio greater than0.2, a 3-methyldodecane to IP-13 weight ratio greater than 0.2, a3-methyldodecane to IP-14 weight ratio greater than 0.2, a3-methyldodecane to IP-15 weight ratio greater than 0.2, a3-methyldodecane to IP-16 weight ratio greater than 0.2, a3-methyldodecane to IP-18 weight ratio greater than 0.2, and a3-methyldodecane to pristane weight ratio greater than 0.2. In someembodiments the condensable hydrocarbon portion may have two or more,three or more or four or more of the weight ratios described above inthe paragraph.

As used in the preceding paragraphs and in the claims with respect toaromatic, cyclic, isoprenoid and normal hydrocarbon compounds, thephrase “one or more” followed by a listing of different compound orcomponent ratios with the last ratio introduced by the conjunction “and”is meant to include a condensable hydrocarbon portion that has at leastone of the listed ratios or that has two or more, or three or more, orfour or more, etc., or all of the listed ratios. Further, a particularcondensable hydrocarbon portion may also have additional ratios ofdifferent compounds or components that are not included in a particularsentence or claim and still fall within the scope of such a sentence orclaim. The embodiments described in the preceding paragraphs may becombined with any of the other aspects of the invention discussedherein. Certain features of the present invention discussed in thepreceding paragraphs are described in terms of a set of numerical upperlimits (e.g. “less than”) and a set of numerical lower limits (e.g.“greater than”) in the preceding paragraph. It should be appreciatedthat ranges formed by any combination of these limits are within thescope of the invention unless otherwise indicated. The embodimentsdescribed in the preceding paragraphs may be combined with any of theother aspects of the invention discussed in such paragraphs or otherwiseherein.

The use of “n-C_” (e.g., n-C10) herein and in the claims is meant torefer to the amount of a particular normal alkane hydrocarbon compoundfound in a condensable hydrocarbon fluid determined by C4-C19 liquidsample gas chromatography (C4-C19 GC) as described herein, particularlyin the section labeled “Experiments” herein. That is “n-C_” isdetermined from the respective C4-C19 peak area determined using theC4-C19 analysis methodology according to the procedure described in theExperiments section of this application. Further, when a particular“n-C_” normal alkane hydrocarbon compound is compared to anotherhydrocarbon compound in a weight ratio herein and in the claims, such aweight ratio is obtained by the ratio of the particular “n-C_” normalalkane hydrocarbon compound's C4-C19 peak area to the other particularhydrocarbon compound's C4-C19 peak area. For example, an n-C8 toethylbenzene weigh ratio is obtained by dividing the n-C8 C4-C19 GC peakarea for a respective condensable hydrocarbon fluid by the C4-C19 GCpeak area for ethylbenzene, where both of such respective C4-C19 GC peakareas are determined by the C4-C19 GC analysis procedures, C4-C19 GCpeak identification methodologies, and C4-C19 GC peak integrationmethodologies discussed in the Experiments section herein.

As used herein and in the claims, weight ratios of aromatic hydrocarboncompounds (e.g., toluene, ortho-xylene, or 1,2,4-trimethylbenzene),cyclic hydrocarbon compounds (e.g., 1,3-dimethyl cyclopentane, ethylcyclopentane, or ethyl cyclohexane) and isoprenoid compounds (e.g.,IP-9, IP-11, or pristane) is meant to refer to the amount of aparticular hydrocarbon compound found in a condensable hydrocarbon fluidas determined by C4-C19 liquid sample gas chromatography (C4-C19 GC) asdescribed herein, particularly in the section labeled “Experiments”herein. That is the amount of a respective compound is determined fromthe respective C4-C19 peak area determined using the C4-C19 analysismethodology according to the procedure described in the Experimentssection of this application. Further, when a first hydrocarbon compoundis compared to a second hydrocarbon compound in a weight ratio hereinand in the claims, such a weight ratio is obtained by the ratio of thefirst hydrocarbon compound's C4-C19 peak area to the second hydrocarboncompound's C4-C19 peak area. For example, an n-C9 to IP-9 weigh ratio isobtained by dividing the n-C9 C4-C19 GC peak area for a respectivecondensable hydrocarbon fluid by the C4-C19 GC peak area for IP-9, whereboth of such respective C4-C19 GC peak areas are determined by theC4-C19 GC analysis procedures, C4-C19 GC peak identificationmethodologies, and C4-C19 GC peak integration methodologies discussed inthe Experiments section herein.

Certain hydrocarbon compounds, particularly certain stereoisomers ofcertain hydrocarbon compounds, can be used for a variety of purposesincluding, for example: determine the relative age of naturallyoccurring petroleum deposits, characterizing the source kerogen ofnaturally occurring oils, and estimating the level of thermal maturationof a naturally occurring oil or kerogen. Examples of such techniques canbe found in Peters, K. E., Walters, C. C., and Moldowan, J. M., TheBiomarker Guide, Vol. 1 & 2, Cambridge University Press (2005).Applicants have investigated certain biomarkers for the hydrocarbonfluids produced in Examples 6-19 and the liquid chromatographicextraction described in Example 20, and some of the biomarker datagenerated in such experiments is presented in FIGS. 53-59.

Hopanes, steranes and phenanthrenes are hydrocarbon molecules that showsystematic isomerization reactions governed by thermal maturation innatural hydrocarbon systems. Hopanes, and steranes like many moleculesof biologic origin, are generally found in certain stereoisomer forms inbiological matter. The biological stereoisomers may be a lessthermodynamically stable form of the compound, but are generatedenzymatically for a specific biological function in a living organism.As the biological matter is altered by diagenesis, catagenesis, andmetagenesis additional stereoisomeric compounds may be formed as thebiological stereoisomeric form is transformed into morethermodynamically stable isomers. Moreover, the amount of a particularbiological compound or derivative thereof present in a source rock orpetroleum deposit may be reduced or eliminated by diagenesis,catagenesis, and metagenesis. Generally the proportion of a geologic,more thermodynamically stable stereoisomer relative to the proportion ofthe biological, less thermodynamically stable stereoisomer in a sourcerock or naturally occurring petroleum deposit can be used to gauge theamount of maturation of such source rock or petroleum deposit.Methylated phenanthrenes behave in a similar fashion during progressivematuration with certain attachment sites for the methyl group favoredwithin certain maturation ranges.

FIG. 53 is a plot of the weight ratio of trisnorhopane maturable (Tm) totrisnorhopane maturable (Tm) plus trisnorhopane stable (Ts) orcollectively (Tm to Tm+Ts) for examples 6-20. The y-axis 520 is theweight ratio of Tm to Tm+Ts which is a measure of the biological isomerTm relative to the thermodynamically favored compound Ts. Thus a moregeologically matured hydrocarbon substance would have a lower Tm toTm+Ts ratio, while an immature biological hydrocarbon substance would beexpected to have a Tm to Tm+Ts ratio of about 1. The x-axis 521 containsthe experiment number from Examples 6-20. As can be seen the Examplenumbers have been consistently ordered on the x-axis from Example 6 toExample 19 in a manner consistent with the ordering of FIGS. 33, 35, 37and 38 in order to relate the data in such figures to the data containedin FIGS. 53-59. In addition, following Example 19 is Example 20 whichincludes the unheated oil shale extraction described in Example 20 inthe Experiments section. This same ordering of the x-axis will be usedconsistently in all of FIGS. 53-59. As can be seen from the graph points522, all of the data for stressed Examples 8-12 at 375° C. and stressedExamples 15-19 at 393° C. generally fall in the same range of about0.975 to 0.985. It is also evident that the 0 psi stressed experimentsfrom Examples 6, 7, 13 and 14 are on the lower end of the scale, withExamples 13 and 14 being the only data points below 0.97. Further, it isapparent that the bitumen extracted from unheated oil shale in Example20 is considerable higher at about 1.0 as would be expected for animmature petroleum hydrocarbon. From the literature, for example Peters,K. E., Walters, C. C., and Moldowan, J. M., The Biomarker Guide,Biomarkers and Isotopes in Petroleum Exploration and Earth History, Vol.2, Cambridge University Press (2005), naturally occurring petroleum oildeposits generally have a Tm to Tm+Ts of 0.6 or less. Thus thehydrocarbon fluid produced in Examples 6-20 is between the immatureextracted bitumen and the more matured naturally occurring petroleumhydrocarbon deposits. It is also apparent that the hydrocarbon fluidsproduced in Examples 6-20 are much more bitumen-like than like naturallyoccurring petroleum hydrocarbon deposits in terms of their Tm to Tm+Tsratio. Further, the unstressed experiments produced a hydrocarbon fluidthat is generally more matured than the stressed experiments.

FIG. 54 is a plot of the weight ratio of stereoisomers of the C-29pentacyclic alkanes that are the most abundant triterpanes found insediments and crude oils. Specifically the plot shows the weight ratioof C-29 17α(H), 21β(H) hopane to C-29 17α(H), 21β(H) hopane plus C-2917β(H), 21β(H) hopane (29H αβ/29H αβ+29H ββ) for examples 6-20. They-axis 530 is the weight ratio of 29H αβ to 29H αβ+29H ββ which is ameasure of the thermodynamically stable isomer of C-29 hopane (29H αβ)relative to the biological form of C-29 hopane (29H ββ). Thus a moregeologically matured hydrocarbon substance would have a higher 29H αβ to29H αβ+29H ββ ratio of about 1 indicating little or none of the 29ββisomer is present, while an immature biological hydrocarbon substancewould be expected to have a lower 29H αβ to 29H αβ+29H ββ ratio of lessthan 1. The x-axis 531 contains the experiment number from Example 6-20in the order described for FIG. 53. As can be seen from the graph points532, all of the data for the heating experiments of Examples 6-19generally fall in the same range of about 0.3 to 0.45. Further, it isapparent that the bitumen extracted from unheated oil shale in Example20 is considerable lower at about 0.17. From the literature, naturallyoccurring petroleum oil deposits generally have a 29H αβ to 29H αβ+29Hββ ratio of about 1, indicating that there is little or none of the 29Hββ isomer present. Thus the hydrocarbon fluids produced in Examples 6-19are between the unmatured extracted bitumen and more matured naturallyoccurring petroleum hydrocarbon oil deposits with respect to the amountof the 29H ββ isomer present. Further, the hydrocarbon fluids producedin Examples 6-19 are more bitumen-like than like naturally occurringpetroleum hydrocarbon oil deposits based on the amount of the 29H ββisomer present.

FIG. 55 is a plot of the stereoisomers of the C-30 pentacyclic alkanesthat are the most abundant triterpanes found in sediments and crudeoils. Specifically the plot shows the weight ratio of C-30 17α(H),21β(H) hopane to C-30 17α(H), 21β(H) hopane plus C-30 17β(H), 21β(H)hopane (30H αβ/30H αβ+30H ββ) for examples 6-20. The y-axis 550 is theweight ratio of 30H αβ to 30H αβ+30H ββ which is a measure of thethermodynamically stable isomer of C-30 hopane (30H αβ) relative to thebiological form of C-30 hopane (30H β(3). Thus a more maturedhydrocarbon substance would have a higher 30H αβ to 30H αβ+30H ββ ratioof about 1 indicating little or none of the 30H ββ isomer is present,while an immature biological hydrocarbon substance would be expected tohave a lower 30H αβ to 30H αβ+30H ββ ratio of less than 1. The x-axis551 contains the experiment number from Example 6-20 in the orderdescribed for FIG. 53. As can be seen from the graph points 552, all ofthe data for the heating experiments of Examples 6-19 generally fall inthe same range of about 0.44 to 0.57. Further, it is apparent that thebitumen extracted from unheated oil shale in Example 20 is slightlyhigher at about 0.62. From the literature, naturally occurring petroleumdeposits generally have a 30H αβ to 30H αβ+30H ββ of about 1, indicatingthat there is little or none of the 30H ββ isomer present. Thus thehydrocarbon fluids produced in Examples 6-19 are similar to the lessmatured extracted bitumen in terms of the amount of the 30H ββ isomerpresent. Further, the hydrocarbon fluids produced in Examples 6-19 havemore of the 30H ββ isomer present than a more matured naturallyoccurring petroleum hydrocarbon oil deposit. In addition the hydrocarbonfluids produced in Examples 6-19 are more bitumen-like than likenaturally occurring petroleum hydrocarbon oil deposits.

FIG. 56 is a plot of the stereoisomers of the C-31 pentacyclic alkanesthat are the most abundant triterpanes found in sediments and crudeoils. Specifically the plot shows the weight ratio of C-31 17α(H),21β(H), 22S homohopane to C-31 17α(H), 21β(H), 22S homohopane plus C-3117α(H), 21β(H), 22R homohopane (31H-S/31H-S+31H-R) for examples 6-20.The y-axis 560 is the weight ratio of 31H-S to 31H-S plus 31H-R which isa measure of the thermodynamically stable isomer of C-31 homohopane31H-S relative to the biological isomer, 31H-R. Thus a more maturedhydrocarbon substance would be expected to have a higher X31H-S to 31H-Splus 31H-R ratio, while a less matured biological hydrocarbon substancewould be expected to have a lower 31H-S to 31H-S plus 31H-R ratio. Thex-axis 561 contains the experiment number from Example 6-20 in the orderdescribed for FIG. 53. As can be seen from the graph points 562, all ofthe data for the stressed Examples 8-12 at 375° C. and stressed Examples15-19 at 393° C. generally fall in the same range of about 0.42 to 0.5.It is also evident that the 0 psi stressed experiments from Examples 6,7, 13 and 14 are on the upper end of the scale, with all such Examplesfalling above 0.52 all the way up to about 0.65 for Examples 13 & 14.Further, it is apparent that the bitumen extracted from unheated oilshale in Example 20 is considerable lower at about 0.25. From theliterature, naturally occurring petroleum deposits generally have a(31H-S/31H-S+31H-R) ranging from about 0.58 to 0.63 (Seifert, W. K., andMoldowan, J. M., The Effect of Thermal Stress on Source-rock Quality asMeasured by Hopane Stereochemistry, Physics and Chemistry of the Earth,12, 229-237 (1980)). Thus with respect to the presence of 31H-S to 31H-Splus 31H-R ratio, the hydrocarbon fluids produced in the stressedExamples 8-12 and 15-19 are close to but less than what is expected fornaturally occurring petroleum hydrocarbon oil deposits. Further, theunstressed experiments produced a hydrocarbon fluid that is most likenaturally occurring oils. In addition, it is apparent that with respectto the presence of the 31H-R isomer of C-31 homohopane, the hydrocarbonfluids produced in Examples 6-19 are more like naturally occurringpetroleum hydrocarbon oil deposits than like bitumen.

FIG. 57 is a plot of the weight ratio of the C-29 5α, 14α, 17α(H) 20Rsteranes to the C-29 5α, 14α, 17α(H) 20R steranes plus the C-29 5α, 14α,17α(H) 20S steranes (C-29 ααα S/C-29 ααα S+C-29 ααα R) for examples6-20. The y-axis 570 is the weight ratio of C-29 ααα S to C-29 ααα Splus C-29 ααα R which is a measure of the thermodynamically stableisomer of C-29 sterane (C-29 ααα S) relative to the biological isomer ofC-29 sterane (C-29 ααα R). Thus a more matured hydrocarbon substancewould be expected to have a higher C-29 ααα S to C-29 ααα S plus C-29ααα R ratio, while an immature hydrocarbon substance would be expectedto have a lower C-29 ααα S to C-29 ααα S plus C-29 ααα R ratio. Thex-axis 571 contains the experiment number from Example 6-20 in the orderdescribed for FIG. 53. As can be seen from the graph points 572, all ofthe data for the for stressed Examples 8-12 at 375° C. and stressedExamples 15-19 at 393° C. generally fall in the same range of about 0.22to 0.3. It is also evident that the 0 psi stressed experiments fromExamples 6, 7, 13 and 14 are on the upper end of the scale, with allsuch Examples falling above 0.36 all the way up to about 0.41 forExamples 13 & 14. Further, it is apparent that the bitumen extractedfrom unheated oil shale in Example 20 is in the same range as thestressed experiments at about 0.26. From the literature, naturallyoccurring petroleum deposits generally have an equilibrium C-29 ααα S toC-29 ααα S plus C-29 ααα R ratio of about 0.5. Thus with respect to thepresence of C-29 ααα S relative to C-29 ααα R, the hydrocarbon fluidsproduced in the stressed Examples 8-12 and 15-19 have ratios much lowerthan what is expected for naturally occurring petroleum hydrocarbon oildeposits and are essentially the same as the source rock bitumen.Further, the unstressed experiments produced hydrocarbon fluids haveratios that are more like naturally occurring oils.

FIG. 58 is a plot of the C-29 5α, 14β, 17β(H) 20S plus C-29 5α, 14β,17β(H) 20R steranes to the C-29 5α, 14β, 17β(H) 20S plus C-29 5α, 14β,17β(H) 20R steranes plus C-29 5α, 14α, 17α(H) 20S plus C-29 5α, 14α,17α(H) 20R steranes (C-29 αββ S&R/C-29αββ S&R+C-29 ααα S&R) for examples6-20. The y-axis 580 is the weight ratio of C-29αββ S&R to C-29 αββ S&Rplus C-29 ααα S&R which is a measure of the thermodynamically stableisomers of the C-29 steranes (C-29 αββ S&R) relative to the biologicalisomers of C-29 sterane (,C-29 ααα S&R). Thus a more matured hydrocarbonsubstance would be expected to have a higher C-29 αββ S&R to C-29 αββS&R plus C-29 ααα S&R ratio, while an immature biological hydrocarbonsubstance would be expected to have a lower C-29 αββ S&R to C-29αββ S&Rplus C-29 ααα S&R ratio. The x-axis 581 contains the experiment numberfrom Example 6-20 in the order described for FIG. 53. As can be seenfrom the graph points 582, all of the data for the for stressed Examples8-12 at 375° C. and stressed Examples 15-19 at 393° C. generally fall inthe same range of about 0.17 to 0.22. It is also evident that the 0 psistressed experiments from Examples 6, 7, 13 and 14 are on the upper endof the scale, with all such Examples falling above 0.24 all the way upto about 0.29 for Example 13. Further, it is apparent that the bitumenextracted from unheated oil shale in Example 20 is slightly lower thanthe stressed experiments at about 0.16. From the literature, naturallyoccurring oils reach an equilibrium C-29 αββ S&R to C-29 αββ S&R plusC-29 ααα S&R ratio of ˜0.75. Thus with respect to the C-29 αββS&R toC-29 αββ S&R plus C-29 ααα S&R ratio, the hydrocarbon fluid produced inthe stressed Examples 8-12 and 15-19 have ratios much lower than what isexpected for naturally occurring oils. Further, the unstressedexperiments produced a hydrocarbon fluid that is more like naturallyoils but still quite distinct.

FIG. 59 is a plot of the weight ratio of 3-methyl phenanthrene(3-MP)+2-methyl phenanthrene (2-MP) to 1-methyl phenanthrene(1-MP)+9-methyl phenanthrene (9-MP) for examples 6-20. The y-axis 590 isthe weight ratio of (3-MP+2-MP) to (1-MP+9-MP) which is a measure of thehigher temperature stability forms of methyl phenanthrene (3-MP+2-MP)relative to the lower temperature stability forms of methyl phenanthrene(1-MP+9-MP). Thus a less matured hydrocarbon substance would be expectedto have a lower (3-MP+2-MP) to (1-MP+9-MP) ratio, while a more maturedhydrocarbon substance would be expected to have a higher (3-MP+2-MP) to(1-MP+9-MP) ratio—for maturities within the oil generation window. Thex-axis 591 contains the experiment number from Example 6-20 in the orderdescribed for FIG. 53. As can be seen from the graph points 592, all ofthe data for the heating experiments of Examples 6-19 generally fall inthe range of about 1.5 to 2.25. Further, it is apparent that the bitumenextracted from unheated oil shale in Example 20 is considerable lower atabout 0.4. From the literature (e.g. Radke, M., Organic Geochemistry ofAromatic Hydrocarbons, Adv. in Petroleum Geochemistry vol. 2, Ed: JimBrooks and Dietrich Welte, Academic Press, London (1987) p. 141-208.),naturally occurring petroleum deposits generally have a (3-MP+2-MP) to(1-MP+9-MP) of about 0.4-0.5 for immature materials like bitumen andabout 0.6-1.5 for naturally occurring petroleum hydrocarbon oildeposits. Thus, indicating that there is more 3-MP+2-MP present as thenaturally occurring petroleum hydrocarbon becomes more matured. Thus,the hydrocarbon fluids produced in Examples 6-19 havemethyl-phenanthrene ratios unlike both bitumen and naturally occurringoils.

From the above-described data discussed in FIGS. 53-59, it can be seenthat hydrocarbon fluids produced by pyrolysis under stress loading havecertain maturity characteristics as judged by the sterochemicalbiomarker ratio and methyl phenanthrene relationships discussed above.In many cases the presence or absence of stress loading also correlatesto step changes in particular biomarker relationships. Some of thehydrocarbon fluid produced from pyrolysis of oil shale shows a morebitumen-like characteristic for some of the above-described biomarkerrelationships, while for other relationships the produced hydrocarbonfluid is, more like a naturally occurring petroleum hydrocarbon oil.Further, some of the hydrocarbon fluid produced from pyrolysis of oilshale is neither bitumen-like nor like naturally occurring petroleumhydrocarbon oil for some of the above-described relationships. Thisimplies that the composition of the produced hydrocarbon fluid from insitu heating and pyrolysis processes will be unlike naturally occurringpetroleum hydrocarbon deposits and also unlike shale oil produced in anex-situ retorting process.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have a (trisnorhopane maturable (Tm)) to(trisnorhopane maturable (Tm)+trisnorhopane stable (Ts)) oralternatively (Tm/Tm+Ts) weight ratio greater than 0.7. In alternateembodiments the condensable hydrocarbon portion may have a(trisnorhopane maturable) to (trisnorhopane maturable+trisnorhopanestable) weight ratio greater than 0.8, 0.9 or 0.95. In alternateembodiments the condensable hydrocarbon portion may have a(trisnorhopane maturable) to (trisnorhopane maturable+trisnorhopanestable) weight ratio between 0.7 and 0.995, between 0.8 and 0.990, orbetween 0.7 and 0.995.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have a [C-29 17α(H), 21β(H) hopane] to [C-2917α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29Hαβ/29H αβ+29H ββ) weight ratio less than 0.9. In alternate embodimentsthe condensable hydrocarbon portion may have a [C-29 17α(H), 21β(H)hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane]weight ratio less than 0.8, 0.7 or 0.6. In alternate embodiments thecondensable hydrocarbon portion may have a [C-29 17α(H), 21β(H) hopane]to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] weight ratiobetween 0.2 and 0.9, between 0.25 and 0.6, or between 0.3 and 0.5.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have a [C-30 17α(H), 21β(H) hopane] to [C-3017α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30Hαβ/30H αβ+30H ββ) weight ratio less than 0.9. In alternate embodimentsthe condensable hydrocarbon portion may have a [C-30 17α(H), 21β(H)hopane] to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane]weight ratio less than 0.8, 0.7 or 0.6. In alternate embodiments thecondensable hydrocarbon portion may have a [C-30 17α(H), 21β(H) hopane]to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] weight ratiobetween 0.3 and 0.62, between 0.35 and 0.60, or between 0.4 and 0.58.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have a [C-31 17α(H), 21β(H), 22S homohopane] to[C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22Rhomohopane] or alternatively (31H-S/31H-S+31H-R) weight ratio less than0.6. In alternate embodiments the condensable hydrocarbon portion mayhave a [C-31 17α(H), 21β(H), 22S homohopane] to [C-31 17α(H), 21β(H),22S homohopane+C-31 17α(H), 21β(H), 22R homohopane] weight ratio lessthan 0.58, 0.55 or 0.50. In alternate embodiments the condensablehydrocarbon portion may have a [C-31 17α(H), 21β(H), 22S homohopane] to[C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22Rhomohopane] weight ratio between 0.25 and 0.6, between 0.3 and 0.58, orbetween 0.4 and 0.55.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have a [C-29 5α, 14α, 17α(H) 20R steranes] to[C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14 α, 17α(H) 20S steranes]or alternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio lessthan 0.7. In alternate embodiments the condensable hydrocarbon portionmay have a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α, 17α(H)20R steranes+C-29 5α, 14 α, 17α(H) 20S steranes] weight ratio less than0.6, 0.5 or 0.4. In alternate embodiments the condensable hydrocarbonportion may have a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α,17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] weight ratiobetween 0.2 and 0.7, between 0.25 and 0.5, or between 0.25 and 0.3.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β,17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H)20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes]or alternatively (C-29αββ S&R/C-29αββ S&R+C-29ααα S&R) weight ratio lessthan 0.7. In alternate embodiments the condensable hydrocarbon portionmay have a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes]to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α,14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] weight ratio lessthan 0.6, 0.4, 0.25 or 0.24. In alternate embodiments the condensablehydrocarbon portion may have a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β,17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H)20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes]weight ratio between 0.15 and 0.7, between 0.17 and 0.5, or between 0.17and 0.25.

In some embodiments, the produced hydrocarbon fluid includes acondensable hydrocarbon portion. In some embodiments the condensablehydrocarbon portion may have a [3-methyl phenanthrene (3-MP)+2-methylphenanthrene (2-MP)]/[1-methyl phenanthrene (1-MP)+9-methyl phenanthrene(9-MP)] weight ratio greater than 0.5. In alternate embodiments thecondensable hydrocarbon portion may have a [3-methyl phenanthrene(3-MP)+2-methyl phenanthrene (2-MP)]/[1-methyl phenanthrene(1-MP)+9-methyl phenanthrene (9-MP)] weight ratio greater than 0.75, 1.0or 1.25. In alternate embodiments the condensable hydrocarbon portionmay have a [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene(2-MP)]/[1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)]weight ratio between 0.5 and 3.0, between 1.0 and 2.5, or between 1.25and 2.5.

In some embodiments the condensable hydrocarbon portion may have one ormore of a (trisnorhopane maturable (Tm)) to (trisnorhopane maturable(Tm)+trisnorhopane stable (Ts)) or alternatively (Tm/Tm+Ts) weight ratiogreater than 0.7, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H)hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29H αβ/29H αβ+29Hββ3) weight ratio less than 0.9, a [C-30 17α(H), 21β(H) hopane] to [C-3017α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30Hαβ/30H αβ+30H ββ) weight ratio less than 0.9, a [C-31 17α(H), 21β(H),22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H),21β(H), 22R homohopane] or alternatively (31H-S/31H-S+31H-R) weightratio less than 0.6, a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α,14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] oralternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio less than0.7, a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to[C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α,14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] or alternatively(C-29αββ S&R/C-29αββ S&R+C-29 ααα S&R) weight ratio less than 0.7, and a[3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)] to [1-methylphenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratio greaterthan 0.5. In some embodiments the condensable hydrocarbon portion mayhave two or more, three or more or four or more of the weight ratiosdescribed above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a (trisnorhopane maturable (Tm)) to (trisnorhopane maturable(Tm)+trisnorhopane stable (Ts)) or alternatively (Tm/Tm+Ts) weight ratiogreater than 0.8, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H)hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29H αβ/29H αβ+29Hββ) weight ratio less than 0.8, a [C-30 17α(H), 21β(H) hopane] to [C-3017α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30Hαβ/30H αβ+30H β(3) weight ratio less than 0.8, a [C-31 17α(H), 21β(H),22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H),21β(H), 22R homohopane] or alternatively (31H-S/31H-S+31H-R) weightratio less than 0.58, a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α,14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] oralternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio less than0.6, a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to[C-29 5α, 14β, 17β (H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α,14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] or alternatively(C-29 αββ S&R/C-29αββ S&R+C-29 ααα S&R) weight ratio less than 0.6, anda [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)] to[1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratiogreater than 0.75. In some embodiments the condensable hydrocarbonportion may have two or more, three or more or four or more of theweight ratios described above in the paragraph.

In some embodiments the condensable hydrocarbon portion may have one ormore of a (trisnorhopane maturable (Tm)) to (trisnorhopane maturable(Tm)+trisnorhopane stable (Ts)) or alternatively (Tm/Tm+Ts) weight ratiogreater than 0.7, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H)hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29H αβ/29H αβ+29Hββ) weight ratio less than 0.7, a [C-30 17α(H), 21β(H) hopane] to [C-3017α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30Hαβ/30H αβ+30H ββ) weight ratio less than 0.7, a [C-31 17α(H), 21β(H),22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H),21β(H), 22R homohopane] or alternatively (31H-S/31H-S+31H-R) weightratio less than 0.55, a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α,14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] oralternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio less than0.5, a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to[C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α,14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] or alternatively(C-29αββ S&R/C-29 αββ S&R+C-29 ααα S&R) weight ratio less than 0.55, anda [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)] to[1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratiogreater than 0.1.0. In some embodiments the condensable hydrocarbonportion may have two or more, three or more or four or more of theweight ratios described above in the paragraph.

As used in the preceding paragraphs and in the claims with respect tohopanes, steranes and phenanthrenes, the phrase “one or more” followedby a listing of different compound or component ratios with the lastratio introduced by the conjunction “and” is meant to include acondensable hydrocarbon portion that has at least one of the listedratios or that has two or more, or three or more, or four or more, etc.,or all of the listed ratios. Further, a particular condensablehydrocarbon portion may also have additional ratios of differentcompounds or components that are not included in a particular sentenceor claim and still fall within the scope of such a sentence or claim.The embodiments described in the preceding paragraphs may be combinedwith any of the other aspects of the invention discussed herein. Certainfeatures of the present invention discussed in the preceding paragraphsare described in terms of a set of numerical upper limits (e.g. “lessthan”) and a set of numerical lower limits (e.g.

“greater than”) in the preceding paragraph. It should be appreciatedthat ranges formed by any combination of these limits are within thescope of the invention unless otherwise indicated. The embodimentsdescribed in the preceding paragraphs may be combined with any of theother aspects of the invention discussed in such paragraphs or otherwiseherein.

As used herein and in the claims, weight ratios of hopanes (e.g., C-2917α(H), 21β(H) hopane), steranes (e.g., C-29 5α, 14α, 17α(H) 20Rsteranes) and phenanthrenes (e.g., 3-methyl phenanthrene) is meant torefer to the amount of a particular hydrocarbon compound found in acondensable hydrocarbon fluid as determined by liquid chromatography(LC) followed by gas chromatography/mass spectrometry (GC/MS) asdescribed herein, particularly in the section labeled “Experiments”herein. That is, the amount of a respective compound is determined fromthe respective GC/MS peak height determined using the LC and GC/MSanalysis methodology according to the procedure described in theExperiments section of this application. Further, when a first compoundis compared to a second compound in a weight ratio herein and in theclaims, such a weight ratio is obtained by the ratio of the firstcompound's GC/MS peak height to the second compound's GC/MS peak height.For example, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H)hopane+C-29 17β(H), 21[3(H) hopane] weigh ratio is obtained by dividingthe [C-29 17α(H), 21β(H) hopane] GC/MS peak height for a respectivecondensable hydrocarbon fluid by the total GC/MS peak height for [C-2917α(H), 21β(H) hopane] and [C-29 17β(H), 21β(H) hopane], where both ofsuch respective GC/MS peak heights are determined by the by liquidchromatography (LC) and gas chromatography/mass spectrometry (GC/MS)analysis procedures, GC/MS peak identification methodologies, and GC/MSpeak measurement methodologies discussed in the Experiments sectionherein.

The discovery that lithostatic stress can affect the composition ofproduced fluids generated within an organic-rich rock via heating andpyrolysis implies that the composition of the produced hydrocarbon fluidcan also be influenced by altering the lithostatic stress of theorganic-rich rock formation. For example, the lithostatic stress of theorganic-rich rock formation may be altered by choice of pillargeometries and/or locations and/or by choice of heating and pyrolysisformation region thickness and/or heating sequencing.

Pillars are regions within the organic-rich rock formation leftunpyrolized at a given time to lessen or mitigate surface subsidence.Pillars may be regions within a formation surrounded by pyrolysisregions within the same formation. Alternatively, pillars may be part ofor connected to the unheated regions outside the general developmentarea. Certain regions that act as pillars early in the life of aproducing field may be converted to producing regions later in the lifeof the field.

Typically in its natural state, the weight of a formation's overburdenis fairly uniformly distributed over the formation. In this state thelithostatic stress existing at particular point within a formation islargely controlled by the thickness and density of the overburden. Adesired lithostatic stress may be selected by analyzing overburdengeology and choosing a position with an appropriate depth and position.

Although lithostatic stresses are commonly assumed to be set by natureand not changeable short of removing all or part of the overburden,lithostatic stress at a specific location within a formation can beadjusted by redistributing the overburden weight so it is not uniformlysupported by the formation. For example, this redistribution ofoverburden weight may be accomplished by two exemplary methods. One orboth of these methods may be used within a single formation. In certaincases, one method may be primarily used earlier in time whereas theother may be primarily used at a later time. Favorably altering thelithostatic stress experienced by a formation region may be performedprior to instigating significant pyrolysis within the formation regionand also before generating significant hydrocarbon fluids. Alternately,favorably altering the lithostatic stress may be performedsimultaneously with the pyrolysis.

A first method of altering lithostatic stress involves making a regionof a subsurface formation less stiff than its neighboring regions.Neighboring regions thus increasingly act as pillars supporting theoverburden as a particular region becomes less stiff. These pillarregions experience increased lithostatic stress whereas the less stiffregion experiences reduced lithostatic stress. The amount of change inlithostatic stress depends upon a number of factors including, forexample, the change in stiffness of the treated region, the size of thetreated region, the pillar size, the pillar spacing, the rockcompressibility, and the rock strength. In an organic-rich rockformation, a region within a formation may be made to experiencemechanical weakening by pyrolyzing the region and creating void spacewithin the region by removing produced fluids. In this way a regionwithin a formation may be made less stiff than neighboring regions thathave not experienced pyrolysis or have experienced a lesser degree ofpyrolysis or production.

A second method of altering lithostatic stress involves causing a regionof a subsurface formation to expand and push against the overburden withgreater force than neighboring regions. This expansion may remove aportion of the overburden weight from the neighboring regions thusincreasing the lithostatic stress experienced by the heated region andreducing the lithostatic stress experienced by neighboring regions. Ifthe expansion is sufficient, horizontal fractures will form in theneighboring regions and the contribution of these regions to supportingthe overburden will decrease. The amount of change in lithostatic stressdepends upon a number of factors including, for example, the amount ofexpansion in the treated region, the size of the treated region, thepillar size, the pillar spacing, the rock compressibility, and the rockstrength. A region within a formation may be made to expand by heatingit so to cause thermal expansion of the rock. Fluid expansion or fluidgeneration can also contribute to expansion if the fluids are largelytrapped within the region. The total expansion amount may beproportional to the thickness of the heated region. It is noted that ifpyrolysis occurs in the heated region and sufficient fluids are removed,the heated region may mechanically weaken and thus may alter thelithostatic stresses experienced by the neighboring regions as describedin the first exemplary method.

Embodiments of the method may include controlling the composition ofproduced hydrocarbon fluids generated by heating and pyrolysis from afirst region within an organic-rich rock formation by increasing thelithostatic stresses within the first region by first heating andpyrolyzing formation hydrocarbons present in the organic-rich rockformation and producing fluids from a second neighboring region withinthe organic-rich rock formation such that the Young's modulus (i.e.,stiffness) of the second region is reduced.

Embodiments of the method may include controlling the composition ofproduced hydrocarbon fluids generated by heating and pyrolysis from afirst region within an organic-rich rock formation by increasing thelithostatic stresses within the first region by heating the first regionprior to or to a greater degree than neighboring regions within theorganic-rich rock formation such that the thermal expansion within thefirst region is greater than that within the neighboring regions of theorganic-rich rock formation.

Embodiments of the method may include controlling the composition ofproduced hydrocarbon fluids generated by heating and pyrolysis from afirst region within an organic-rich rock formation by decreasing thelithostatic stresses within the first region by heating one or moreneighboring regions of the organic-rich rock formation prior to or to agreater degree than the first region such that the thermal expansionwithin the neighboring regions is greater than that within the firstregion.

Embodiments of the method may include locating, sizing, and/or timingthe heating of heated regions within an organic-rich rock formation soas to alter the in situ lithostatic stresses of current or futureheating and pyrolysis regions within the organic-rich rock formation soas to control the composition of produced hydrocarbon fluids.

Some production procedures include in situ heating of an organic-richrock formation that contains both formation hydrocarbons and formationwater-soluble minerals prior to substantial removal of the formationwater-soluble minerals from the organic-rich rock formation. In someembodiments of the invention there is no need to partially,substantially or completely remove the water-soluble minerals prior toin situ heating. For example, in an oil shale formation that containsnaturally occurring nahcolite, the oil shale may be heated prior tosubstantial removal of the nahcolite by solution mining. Substantialremoval of a water-soluble mineral may represent the degree of removalof a water-soluble mineral that occurs from any commercial solutionmining operation as known in the art. Substantial removal of awater-soluble mineral may be approximated as removal of greater than 5weight percent of the total amount of a particular water-soluble mineralpresent in the zone targeted for hydrocarbon fluid production in theorganic-rich rock formation. In alternative embodiments, in situ heatingof the organic-rich rock formation to pyrolyze formation hydrocarbonsmay be commenced prior to removal of greater than 3 weight percent,alternatively 7 weight percent, 10 weight percent or 13 weight percentof the formation water-soluble minerals from the organic-rich rockformation.

The impact of heating oil shale to produce oil and gas prior toproducing nahcolite is to convert the nahcolite to a more recoverableform (soda ash), and provide permeability facilitating its subsequentrecovery. Water-soluble mineral recovery may take place as soon as theretorted oil is produced, or it may be left for a period of years forlater recovery. If desired, the soda ash can be readily converted backto nahcolite on the surface. The ease with which this conversion can beaccomplished makes the two minerals effectively interchangeable.

In some production processes, heating the organic-rich rock formationincludes generating soda ash by decomposition of nahcolite. The methodmay include processing an aqueous solution containing water-solubleminerals in a surface facility to remove a portion of the water-solubleminerals. The processing step may include removing the water-solubleminerals by precipitation caused by altering the temperature of theaqueous solution.

The water-soluble minerals may include sodium. The water-solubleminerals may also include nahcolite (sodium bicarbonate), soda ash(sodium carbonate), dawsonite (NaAl(CO₃)(OH)₂), or combinations thereof.The surface processing may further include converting the soda ash backto sodium bicarbonate (nahcolite) in the surface facility by reactionwith CO₂. After partial or complete removal of the water-solubleminerals, the aqueous solution may be reinjected into a subsurfaceformation where it may be sequestered. The subsurface formation may bethe same as or different from the original organic-rich rock formation.

In some production processes, heating of the organic-rich rock formationboth pyrolyzes at least a portion of the formation hydrocarbons tocreate hydrocarbon fluids and makes available migratory contaminantspecies previously bound in the organic-rich rock formation. Themigratory contaminant species may be formed through pyrolysis of theformation hydrocarbons, may be liberated from the formation itself uponheating, or may be made accessible through the creation of increasedpermeability upon heating of the formation. The migratory contaminantspecies may be soluble in water or other aqueous fluids present in orinjected into the organic-rich rock formation.

Producing hydrocarbons from pyrolyzed oil shale will generally leavebehind some migratory contaminant species which are at least partiallywater-soluble. Depending on the hydrological connectivity of thepyrolyzed shale oil to shallower zones, these components may eventuallymigrate into ground water in concentrations which are environmentallyunacceptable. The types of potential migratory contaminant speciesdepend on the nature of the oil shale pyrolysis and the composition ofthe oil shale being converted. If the pyrolysis is performed in theabsence of oxygen or air, the contaminant species may include aromatichydrocarbons (e.g. benzene, toluene, ethylbenzene, xylenes),polyaromatic hydrocarbons (e.g. anthracene, pyrene, naphthalene,chrysene), metal contaminants (e.g. As, Co, Pb, Mo, Ni, and Zn), andother species such as sulfates, ammonia, Al, K, Mg, chlorides, flouridesand phenols. If oxygen or air is employed, contaminant species may alsoinclude ketones, alcohols, and cyanides. Further, the specific migratorycontaminant species present may include any subset or combination of theabove-described species.

It may be desirable for a field developer to assess the connectivity ofthe organic-rich rock formation to aquifers. This may be done todetermine if, or to what extent, in situ pyrolysis of formationhydrocarbons in the organic-rich rock formation may create migratoryspecies with the propensity to migrate into an aquifer. If theorganic-rich rock formation is hydrologically connected to an aquifer,precautions may be taken to reduce or prevent species generated orliberated during pyrolysis from entering the aquifer. Alternatively, theorganic-rich rock formation may be flushed with water or an aqueousfluid after pyrolysis as described herein to remove water-solubleminerals and/or migratory contaminant species. In other embodiments, theorganic-rich rock formation may be substantially hydrologicallyunconnected to any source of ground water. In such a case, flushing theorganic-rich rock formation may not be desirable for removal ofmigratory contaminant species but may nevertheless be desirable forrecovery of water-soluble minerals.

Following production of hydrocarbons from an organic-rich formation,some migratory contaminant species may remain in the rock formation. Insuch case, it may be desirable to inject an aqueous fluid into theorganic-rich rock formation and have the injected aqueous fluid dissolveat least a portion of the water-soluble minerals and/or the migratorycontaminant species to form an aqueous solution. The aqueous solutionmay then be produced from the organic-rich rock formation through, forexample, solution production wells. The aqueous fluid may be adjusted toincrease the solubility of the migratory contaminant species and/or thewater-soluble minerals. The adjustment may include the addition of anacid or base to adjust the pH of the solution. The resulting aqueoussolution may then be produced from the organic-rich rock formation tothe surface for processing.

After initial aqueous fluid production, it may further be desirable toflush the matured organic-rich rock zone and the unmatured organic-richrock zone with an aqueous fluid. The aqueous fluid may be used tofurther dissolve water-soluble minerals and migratory contaminantspecies. The flushing may optionally be completed after a substantialportion of the hydrocarbon fluids have been produced from the maturedorganic-rich rock zone. In some embodiments, the flushing step may bedelayed after the hydrocarbon fluid production step. The flushing may bedelayed to allow heat generated from the heating step to migrate deeperinto surrounding unmatured organic-rich rock zones to convert nahcolitewithin the surrounding unmatured organic-rich rock zones to soda ash.Alternatively, the flushing may be delayed to allow heat generated fromthe heating step to generate permeability within the surroundingunmatured organic-rich rock zones. Further, the flushing may be delayedbased on current and/or forecast market prices of sodium bicarbonate,soda ash, or both as further discussed herein. This method may becombined with any of the other aspects of the invention as discussedherein

Upon flushing of an aqueous solution, it may be desirable to process theaqueous solution in a surface facility to remove at least some of themigratory contaminant species. The migratory contaminant species may beremoved through use of, for example, an adsorbent material, reverseosmosis, chemical oxidation, bio-oxidation, and/or ion exchange.Examples of these processes are individually known in the art. Exemplaryadsorbent materials may include activated carbon, clay, or fuller'searth.

In certain areas with oil shale resources, additional oil shaleresources or other hydrocarbon resources may exist at lower depths.Other hydrocarbon resources may include natural gas in low permeabilityformations (so-called “tight gas”) or natural gas trapped in andadsorbed on coal (so called “coal bed methane”). In some embodimentswith multiple shale oil resources it may be advantageous to developdeeper zones first and then sequentially shallower zones. In this way,wells will need not cross hot zones or zones of weakened rock. In otherembodiments in may be advantageous to develop deeper zones by drillingwells through regions being utilized as pillars for shale oildevelopment at a shallower depth.

Simultaneous development of shale oil resources and natural gasresources in the same area can synergistically utilize certain facilityand logistic operations. For example, gas treating may be performed at asingle plant. Likewise personnel may be shared among the developments.

FIG. 6 illustrates a schematic diagram of an embodiment of surfacefacilities 70 that may be configured to treat a produced fluid. Theproduced fluid 85 may be produced from the subsurface formation 84though a production well 71 as described herein. The produced fluid mayinclude any of the produced fluids produced by any of the methods asdescribed herein. The subsurface formation 84 may be any subsurfaceformation, including, for example, an organic-rich rock formationcontaining any of oil shale, coal, or tar sands for example. Aproduction scheme may involve quenching 72 produced fluids to atemperature below 300° F., 200° F., or even 100° F., separating outcondensable components (i.e., oil 74 and water 75) in an oil separator73, treating the noncondensable components 76 (i.e. gas) in a gastreating unit 77 to remove water 78 and sulfur species 79, removing theheavier components from the gas (e.g., propane and butanes) in a gasplant 81 to form liquid petroleum gas (LPG) 80 for sale, and generatingelectrical power 82 in a power plant 88 from the remaining gas 83. Theelectrical power 82 may be used as an energy source for heating thesubsurface formation 84 through any of the methods described herein. Forexample, the electrical power 82 may be feed at a high voltage, forexample 132 kV, to a transformer 86 and let down to a lower voltage, forexample 6600 V, before being fed to an electrical resistance heaterelement located in a heater well 87 located in the subsurface formation84. In this way all or a portion of the power required to heat thesubsurface formation 84 may be generated from the non-condensableportion of the produced fluids 85. Excess gas, if available, may beexported for sale.

Produced fluids from in situ oil shale production contain a number ofcomponents which may be separated in surface facilities. The producedfluids typically contain water, noncondensable hydrocarbon alkanespecies (e.g., methane, ethane, propane, n-butane, isobutane),noncondensable hydrocarbon alkene species (e.g., ethene, propene),condensable hydrocarbon species composed of (alkanes, olefins,aromatics, and polyaromatics among others), CO₂, CO, H₂, H₂S, and NH₃.

In a surface facility, condensable components may be separated fromnon-condensable components by reducing temperature and/or increasingpressure. Temperature reduction may be accomplished using heatexchangers cooled by ambient air or available water. Alternatively, thehot produced fluids may be cooled via heat exchange with producedhydrocarbon fluids previously cooled. The pressure may be increased viacentrifugal or reciprocating compressors. Alternatively, or inconjunction, a diffuser-expander apparatus may be used to condense outliquids from gaseous flows. Separations may involve several stages ofcooling and/or pressure changes.

Water in addition to condensable hydrocarbons may be dropped out of thegas when reducing temperature or increasing pressure. Liquid water maybe separated from condensable hydrocarbons via gravity settling vesselsor centrifugal separators. Demulsifiers may be used to aid in waterseparation.

Methods to remove CO₂, as well as other so-called acid gases (such asH₂S), from produced hydrocarbon gas include the use of chemical reactionprocesses and of physical solvent processes. Chemical reaction processestypically involve contacting the gas stream with an aqueous aminesolution at high pressure and/or low temperature. This causes the acidgas species to chemically react with the amines and go into solution. Byraising the temperature and/or lowering the pressure, the chemicalreaction can be reversed and a concentrated stream of acid gases can berecovered. An alternative chemical reaction process involves hotcarbonate solutions, typically potassium carbonate. The hot carbonatesolution is regenerated and the concentrated stream of acid gases isrecovered by contacting the solution with steam. Physical solventprocesses typically involve contacting the gas stream with a glycol athigh pressure and/or low temperature. Like the amine processes, reducingthe pressure or raising the temperature allows regeneration of thesolvent and recovery of the acid gases. Certain amines or glycols may bemore or less selective in the types of acid gas species removed. Sizingof any of these processes requires determining the amount of chemical tocirculate, the rate of circulation, the energy input for regeneration,and the size and type of gas-chemical contacting equipment. Contactingequipment may include packed or multi-tray countercurrent towers.Optimal sizing for each of these aspects is highly dependent on the rateat which gas is being produced from the formation and the concentrationof the acid gases in the gas stream.

Acid gas removal may also be effectuated through the use of distillationtowers. Such towers may include an intermediate freezing section whereinfrozen CO₂ and H₂₅ particles are allowed to form. A mixture of frozenparticles and liquids fall downward into a stripping section, where thelighter hydrocarbon gasses break out and rise within the tower. Arectification section may be provided at an upper end of the tower tofurther facilitate the cleaning of the overhead gas stream.

The hydrogen content of a gas stream may be adjusted by either removingall or a portion of the hydrogen or by removing all or a portion of thenon-hydrogen species (e.g., CO₂, CH₄, etc.) Separations may beaccomplished using cryogenic condensation, pressure-swing ortemperature-swing adsorption, or selective diffusion membranes. Ifadditional hydrogen is needed, hydrogen may be made by reforming methanevia the classic water-shift reaction.

EXPERIMENTS

Heating experiments were conducted on several different oil shalespecimens and the liquids and gases released from the heated oil shaleexamined in detail. An oil shale sample from the Mahogany formation inthe Piceance Basin in Colorado was collected. A solid, continuous blockof the oil shale formation, approximately 1 cubic foot in size, wascollected from the pilot mine at the Colony mine site on the easternside of Parachute Creek. The oil shale block was designated CM-1B. Thecore specimens taken from this block, as described in the followingexamples, were all taken from the same stratigraphic interval. Theheating tests were conducted using a Parr vessel, model number 243HC5,which is shown in FIG. 18 and is available from Parr Instrument Company.

Example 1

Oil shale block CM-1B was cored across the bedding planes to produce acylinder 1.391 inches in diameter and approximately 2 inches long. Agold tube 7002 approximately 2 inches in diameter and 5 inches long wascrimped and a screen 7000 inserted to serve as a support for the corespecimen 7001 (FIG. 17). The oil shale core specimen 7001, 82.46 gramsin weight, was placed on the screen 7000 in the gold tube 7002 and theentire assembly placed into a Parr heating vessel. The Parr vessel 7010,shown in FIG. 18, had an internal volume of 565 milliliters. Argon wasused to flush the Parr vessel 7010 several times to remove air presentin the chamber and the vessel pressurized to 500 psi with argon. TheParr vessel was then placed in a furnace which was designed to fit theParr vessel. The furnace was initially at room temperature and washeated to 400° C. after the Parr vessel was placed in the furnace. Thetemperature of the Parr vessel achieved 400° C. after about 3 hours andremained in the 400° C. furnace for 24 hours. The Parr vessel was thenremoved from the furnace and allowed to cool to room temperature over aperiod of approximately 16 hours.

The room temperature Parr vessel was sampled to obtain a representativeportion of the gas remaining in the vessel following the heatingexperiment. A small gas sampling cylinder 150 milliliters in volume wasevacuated, attached to the Parr vessel and the pressure allowed toequilibrate. Gas chromatography (GC) analysis testing andnon-hydrocarbon gas sample gas chromatography (GC) (GC not shown) ofthis gas sample yielded the results shown in FIG. 19, Table 2 andTable 1. In FIG. 19 the y-axis 4000 represents the detector response inpico-amperes (pA) while the x-axis 4001 represents the retention time inminutes. In FIG. 19 peak 4002 represents the response for methane, peak4003 represents the response for ethane, peak 4004 represents theresponse for propane, peak 4005 represents the response for butane, peak4006 represents the response for pentane and peak 4007 represents theresponse for hexane. From the GC results and the known volumes andpressures involved the total hydrocarbon content of the gas (2.09grams), CO₂ content of the gas (3.35 grams), and H2S content of the gas(0.06 gram) were obtained.

TABLE 2 Peak and area details for FIG. 19 - Example 1 - 0 stress - gasGC Peak RetTime Area Number [min] [pA*s] Name 1 0.910 1.46868e4 Methane2 0.999 148.12119 ? 3 1.077 1.26473e4 Ethane 4 2.528 1.29459e4 Propane 54.243 2162.93066 iC4 6 4.922 563.11804 ? 7 5.022 5090.54150 n-Butane 85.301 437.92255 ? 9 5.446 4.67394 ? 10 5.582 283.92194 ? 11 6.13515.47334 ? 12 6.375 1159.83130 iC5 13 6.742 114.83960 ? 14 6.8991922.98450 n-Pentane 15 7.023 2.44915 ? 16 7.136 264.34424 ? 17 7.296127.60601 ? 18 7.383 118.79453 ? 19 7.603 3.99227 ? 20 8.138 13.15432 ?21 8.223 13.01887 ? 22 8.345 103.15615 ? 23 8.495 291.26767 2-methylpentane 24 8.651 15.64066 ? 25 8.884 91.85989 ? 26 9.165 40.09448 ? 279.444 534.44507 n-Hexane 28 9.557 2.64731 ? 29 9.650 32.28295 ? 30 9.71452.42796 ? 31 9.793 42.05001 ? 32 9.852 8.93775 ? 33 9.914 4.43648 ? 3410.013 24.74299 ? 35 10.229 13.34387 ? 36 10.302 133.95892 ? 37 10.5772.67224 ? 38 11.252 27.57400 ? 39 11.490 23.41665 ? 40 11.567 8.13992 ?41 11.820 32.80781 ? 42 11.945 4.61821 ? 43 12.107 30.67044 ? 44 12.1782.58269 ? 45 12.308 13.57769 ? 46 12.403 12.43018 ? 47 12.492 34.29918 ?48 12.685 4.71311 ? 49 12.937 183.31729 ? 50 13.071 7.18510 ? 51 13.1552.01699 ? 52 13.204 7.77467 ? 53 13.317 7.21400 ? 54 13.443 4.22721 ? 5513.525 35.08374 ? 56 13.903 18.48654 ? 57 14.095 6.39745 ? 58 14.3223.19935 ? 59 14.553 8.48772 ? 60 14.613 3.34738 ? 61 14.730 5.44062 ? 6214.874 40.17010 ? 63 14.955 3.41596 ? 64 15.082 3.04766 ? 65 15.1387.33028 ? 66 15.428 2.71734 ? 67 15.518 11.00256 ? 68 15.644 5.16752 ?69 15.778 45.12025 ? 70 15.855 3.26920 ? 71 16.018 3.77424 ? 72 16.4844.66657 ? 73 16.559 5.54783 ? 74 16.643 10.57255 ? 75 17.261 2.19534 ?76 17.439 10.26123 ? 77 17.971 1.85618 ? 78 18.097 11.42077 ?

The Parr vessel was then vented to achieve atmospheric pressure, thevessel opened, and liquids collected from both inside the gold tube andin the bottom of the Parr vessel. Water was separated from thehydrocarbon layer and weighed. The amount collected is noted in Table 1.The collected hydrocarbon liquids were placed in a small vial, sealedand stored in the absence of light. No solids were observed on the wallsof the gold tube or the walls of the Parr vessel. The solid corespecimen was weighed and determined to have lost 19.21 grams as a resultof heating. Whole oil gas chromatography (WOGC) testing of the liquidyielded the results shown in FIG. 20, Table 3, and Table 1. In FIG. 20the y-axis 5000 represents the detector response in pico-amperes (pA)while the x-axis 5001 represents the retention time in minutes. The GCchromatogram is shown generally by label 5002 with individual identifiedpeaks labeled with abbreviations.

TABLE 3 Peak and area details for FIG. 20 - Example 1 - 0 stress -liquid GC Ret. Time Peak Area Compound Peak # [min] [pA*s] Name 1 2.660119.95327 iC4 2 2.819 803.25989 nC4 3 3.433 1091.80298 iC5 4 3.7882799.32520 nC5 5 5.363 1332.67871 2-methyl pentane (2MP) 6 5.798466.35703 3-methyl pentane (3MP) 7 6.413 3666.46240 nC6 8 7.3141161.70435 Methyl cyclopentane (MCP) 9 8.577 287.05969 Benzene (BZ) 109.072 530.19781 Cyclohexane (CH) 11 10.488 4700.48291 nC7 12 11.174937.38757 Methyl cyclohexane (MCH) 13 12.616 882.17358 Toluene (TOL) 1414.621 3954.29687 nC8 15 18.379 3544.52905 nC9 16 21.793 3452.04199 nC1017 24.929 3179.11841 nC11 18 27.843 2680.95459 nC12 19 30.571 2238.89600nC13 20 33.138 2122.53540 nC14 21 35.561 1773.59973 nC15 22 37.8521792.89526 nC16 23 40.027 1394.61707 nC17 24 40.252 116.81663 Pristane(Pr) 25 42.099 1368.02734 nC18 26 42.322 146.96437 Phytane (Ph) 2744.071 1130.63342 nC19 28 45.956 920.52136 nC20 29 47.759 819.92810 nC2130 49.483 635.42065 nC22 31 51.141 563.24316 nC23 32 52.731 432.74606nC24 33 54.261 397.36270 nC25 34 55.738 307.56073 nC26 35 57.161298.70926 nC27 36 58.536 252.60083 nC28 37 59.867 221.84540 nC29 3861.154 190.29596 nC30 39 62.539 123.65781 nC31 40 64.133 72.47668 nC3241 66.003 76.84142 nC33 42 68.208 84.35004 nC34 43 70.847 36.68131 nC3544 74.567 87.62341 nC36 45 77.798 33.30892 nC37 46 82.361 21.99784 nC38Totals: 5.32519e4

Example 2

Oil shale block CM-1B was cored in a manner similar to that of Example 1except that a 1 inch diameter core was created. With reference to FIG.21, the core specimen 7050 was approximately 2 inches in length andweighed 42.47 grams. This core specimen 7050 was placed in a Bereasandstone cylinder 7051 with a 1-inch inner diameter and a 1.39 inchouter diameter. Berea plugs 7052 and 7053 were placed at each end ofthis assembly, so that the core specimen was completely surrounded byBerea. The Berea cylinders and plugs were fired at 500° C. for two hoursprior to use with the mini load frame. The Berea cylinder 7051 alongwith the core specimen 7050 and the Berea end plugs 7052 and 7053 wereplaced in a slotted stainless steel sleeve and clamped into place. Thesample assembly 7060 was placed in a spring-loaded mini-load-frame 7061as shown in FIG. 22. Load was applied by tightening the nuts 7062 and7063 at the top of the load frame 7061 to compress the springs 7064 and7065. The springs 7064 and 7065 were high temperature, Inconel springs,which delivered 400 psi effective stress to the oil shale specimen 7060when compressed. Sufficient travel of the springs 7064 and 7065 remainedin order to accommodate any expansion of the core specimen 7060 duringthe course of heating. In order to ensure that this was the case, goldfoil 7066 was placed on one of the legs of the apparatus to gauge theextent of travel. The entire spring loaded apparatus 7061 was placed inthe Parr vessel (FIG. 18) and the heating experiment conducted asdescribed in Example 1.

As described in Example 1, the room temperature Parr vessel was thensampled to obtain a representative portion of the gas remaining in thevessel following the heating experiment. Gas sampling, hydrocarbon gassample gas chromatography (GC) testing, and non-hydrocarbon gas samplegas chromatography (GC) was conducted as in Example 1. Results are shownin FIG. 23, Table 4 and Table 1. In FIG. 23 the y-axis 4010 representsthe detector response in pico-amperes (pA) while the x-axis 4011represents the retention time in minutes. In FIG. 23 peak 4012represents the response for methane, peak 4013 represents the responsefor ethane, peak 4014 represents the response for propane, peak 4015represents the response for butane, peak 4016 represents the responsefor pentane and peak 4017 represents the response for hexane. From thegas chromatographic results and the known volumes and pressures involvedthe total hydrocarbon content of the gas was determined to be 1.33 gramsand CO₂ content of the gas was 1.70 grams.

TABLE 4 Peak and area details for FIG. 23 - Example 2 - 400 psi stress -gas GC Peak RetTime Area Number [min] [pA*s] Name 1 0.910 1.36178e4Methane 2 0.999 309.65613 ? 3 1.077 1.24143e4 Ethane 4 2.528 1.41685e4Propane 5 4.240 2103.01929 iC4 6 4.917 1035.25513 ? 7 5.022 5689.08887n-Butane 8 5.298 450.26572 ? 9 5.578 302.56229 ? 10 6.125 33.82201 ? 116.372 1136.37097 iC5 12 6.736 263.35754 ? 13 6.898 2254.86621 n-Pentane14 7.066 7.12101 ? 15 7.133 258.31876 ? 16 7.293 126.54671 ? 17 7.378155.60977 ? 18 7.598 6.73467 ? 19 7.758 679.95312 ? 20 8.133 27.13466 ?21 8.216 24.77329 ? 22 8.339 124.70064 ? 23 8.489 289.12952 2-methylpentane 24 8.644 19.83309 ? 25 8.878 92.18938 ? 26 9.184 102.25701 ? 279.438 664.42584 n-Hexane 28 9.549 2.91525 ? 29 9.642 26.86672 ? 30 9.70549.83235 ? 31 9.784 52.11239 ? 32 9.843 9.03158 ? 33 9.904 6.18217 ? 3410.004 24.84150 ? 35 10.219 13.21182 ? 36 10.292 158.67511 ? 37 10.4112.49094 ? 38 10.566 3.25252 ? 39 11.240 46.79988 ? 40 11.478 29.59438 ?41 11.555 12.84377 ? 42 11.809 38.67433 ? 43 11.935 5.68525 ? 44 12.09631.29068 ? 45 12.167 5.84513 ? 46 12.297 15.52042 ? 47 12.393 13.54158 ?48 12.483 30.95983 ? 49 12.669 20.21915 ? 50 12.929 229.00655 ? 5113.063 6.38678 ? 52 13.196 10.89876 ? 53 13.306 7.91553 ? 54 13.4355.05444 ? 55 13.516 44.42806 ? 56 13.894 20.61910 ? 57 14.086 8.32365 ?58 14.313 2.80677 ? 59 14.545 9.18198 ? 60 14.605 4.93703 ? 61 14.7225.06628 ? 62 14.865 46.53282 ? 63 14.946 6.55945 ? 64 15.010 2.85594 ?65 15.075 4.05371 ? 66 15.131 9.15954 ? 67 15.331 2.16523 ? 68 15.4213.03294 ? 69 15.511 9.73797 ? 70 15.562 5.22962 ? 71 15.636 3.73105 ? 7215.771 54.64651 ? 73 15.848 3.95764 ? 74 16.010 3.39639 ? 75 16.4775.49586 ? 76 16.552 6.21470 ? 77 16.635 11.08140 ? 78 17.257 2.28673 ?79 17.318 2.82284 ? 80 17.433 11.11376 ? 81 17.966 2.54065 ? 82 18.09014.28333 ?

At this point, the Parr vessel was vented to achieve atmosphericpressure, the vessel opened, and liquids collected from inside the Parrvessel. Water was separated from the hydrocarbon layer and weighed. Theamount collected is noted in Table 1. The collected hydrocarbon liquidswere placed in a small vial, sealed and stored in the absence of light.Any additional liquid coating the surface of the apparatus or sides ofthe Parr vessel was collected with a paper towel and the weight of thiscollected liquid added to the total liquid collected. Any liquidremaining in the Berea sandstone was extracted with methylene chlorideand the weight accounted for in the liquid total reported in Table 1.The Berea sandstone cylinder and end caps were clearly blackened withorganic material as a result of the heating. The organic material in theBerea was not extractable with either toluene or methylene chloride, andwas therefore determined to be coke formed from the cracking ofhydrocarbon liquids. After the heating experiment, the Berea was crushedand its total organic carbon (TOC) was measured. This measurement wasused to estimate the amount of coke in the Berea and subsequently howmuch liquid must have cracked in the Berea. A constant factor of 2.283was used to convert the TOC measured to an estimate of the amount ofliquid, which must have been present to produce the carbon found in theBerea. This liquid estimated is the “inferred oil” value shown inTable 1. The solid core specimen was weighed and determined to have lost10.29 grams as a result of heating.

Example 3

Conducted in a manner similar to that of Example 2 on a core specimenfrom oil shale block CM-1B, where the effective stress applied was 400psi. Results for the gas sample collected and analyzed by hydrocarbongas sample gas chromatography (GC) and non-hydrocarbon gas sample gaschromatography (GC) (GC not shown) are shown in FIG. 24, Table 5 andTable 1. In FIG. 24 the y-axis 4020 represents the detector response inpico-amperes (pA) while the x-axis 4021 represents the retention time inminutes. In FIG. 24 peak 4022 represents the response for methane, peak4023 represents the response for ethane, peak 4024 represents theresponse for propane, peak 4025 represents the response for butane, peak4026 represents the response for pentane and peak 4027 represents theresponse for hexane. Results for the liquid collected and analyzed bywhole oil gas chromatography (WOGC) analysis are shown in FIG. 25, Table6 and Table 1. In FIG. 25 the y-axis 5050 represents the detectorresponse in pico-amperes (pA) while the x-axis 5051 represents theretention time in minutes. The GC chromatogram is shown generally bylabel 5052 with individual identified peaks labeled with abbreviations.

TABLE 5 Peak and area details for FIG. 24 - Example 3 - 400 psi stress -gas GC Peak RetTime Area Number [min] [pA*s] Name 1 0.910 1.71356e4Methane 2 0.998 341.71646 ? 3 1.076 1.52621e4 Ethane 4 2.534 1.72319e4Propane 5 4.242 2564.04077 iC4 6 4.919 1066.90942 ? 7 5.026 6553.25244n-Butane 8 5.299 467.88803 ? 9 5.579 311.65158 ? 10 6.126 33.61063 ? 116.374 1280.77869 iC5 12 6.737 250.05510 ? 13 6.900 2412.40918 n-Pentane14 7.134 249.80679 ? 15 7.294 122.60424 ? 16 7.379 154.40988 ? 17 7.5996.87471 ? 18 8.132 25.50270 ? 19 8.216 22.33015 ? 20 8.339 129.17023 ?21 8.490 304.97903 2-methyl pentane 22 8.645 18.48411 ? 23 8.87998.23043 ? 24 9.187 89.71329 ? 25 9.440 656.02161 n-Hexane 26 9.5513.05892 ? 27 9.645 25.34058 ? 28 9.708 45.14915 ? 29 9.786 48.62077 ? 309.845 10.03335 ? 31 9.906 5.43165 ? 32 10.007 22.33582 ? 33 10.21916.02756 ? 34 10.295 196.43715 ? 35 10.413 2.98115 ? 36 10.569 3.88067 ?37 11.243 41.63386 ? 38 11.482 28.44063 ? 39 11.558 12.05196 ? 40 11.81237.83630 ? 41 11.938 5.45990 ? 42 12.100 31.03111 ? 43 12.170 4.91053 ?44 12.301 15.75041 ? 45 12.397 13.75454 ? 46 12.486 30.26099 ? 47 12.67215.14775 ? 48 12.931 207.50433 ? 49 13.064 3.35393 ? 50 13.103 3.04880 ?51 13.149 1.62203 ? 52 13.198 7.97665 ? 53 13.310 7.49605 ? 54 13.4374.64921 ? 55 13.519 41.82572 ? 56 13.898 19.01739 ? 57 14.089 7.34498 ?58 14.316 2.68912 ? 59 14.548 8.29593 ? 60 14.608 3.93147 ? 61 14.7254.75483 ? 62 14.869 40.93447 ? 63 14.949 5.30140 ? 64 15.078 5.79979 ?65 15.134 7.95179 ? 66 15.335 1.91589 ? 67 15.423 2.75893 ? 68 15.5158.64343 ? 69 15.565 3.76481 ? 70 15.639 3.41854 ? 71 15.774 45.59035 ?72 15.850 3.73501 ? 73 16.014 5.84199 ? 74 16.480 4.87036 ? 75 16.5555.12607 ? 76 16.639 9.97469 ? 77 17.436 8.00434 ? 78 17.969 3.86749 ? 7918.093 9.71661 ?

TABLE 6 Peak and area details from FIG. 25 - Example 3 - 400 psistress - liquid GC. RetTime Peak Area Compound Peak # [min] [pA*s] Name1 2.744 102.90978 iC4 2 2.907 817.57861 nC4 3 3.538 1187.01831 iC5 43.903 3752.84326 nC5 5 5.512 1866.25342 2MP 6 5.950 692.18964 3MP 76.580 6646.48242 nC6 8 7.475 2117.66919 MCP 9 8.739 603.21204 BZ 109.230 1049.96240 CH 11 10.668 9354.29590 nC7 12 11.340 2059.10303 MCH 1312.669 689.82861 TOL 14 14.788 8378.59375 nC8 15 18.534 7974.54883 nC916 21.938 7276.47705 nC10 17 25.063 6486.47998 nC11 18 27.970 5279.17187nC12 19 30.690 4451.49902 nC13 20 33.254 4156.73389 nC14 21 35.6723345.80273 nC15 22 37.959 3219.63745 nC16 23 40.137 2708.28003 nC17 2440.227 219.38252 Pr 25 42.203 2413.01929 nC18 26 42.455 317.17825 Ph 2744.173 2206.65405 nC19 28 46.056 1646.56616 nC20 29 47.858 1504.49097nC21 30 49.579 1069.23608 nC22 31 51.234 949.49316 nC23 32 52.823719.34735 nC24 33 54.355 627.46436 nC25 34 55.829 483.81885 nC26 3557.253 407.86371 nC27 36 58.628 358.52216 nC28 37 59.956 341.01791 nC2938 61.245 214.87863 nC30 39 62.647 146.06461 nC31 40 64.259 127.66831nC32 41 66.155 85.17574 nC33 42 68.403 64.29253 nC34 43 71.066 56.55088nC35 44 74.282 28.61854 nC36 45 78.140 220.95929 nC37 46 83.075 26.95426nC38 Totals: 9.84518e4

Example 4

Conducted in a manner similar to that of Example 2 on a core specimenfrom oil shale block CM-1B; however, in this example the appliedeffective stress was 1,000 psi. Results for the gas collected andanalyzed by hydrocarbon gas sample gas chromatography (GC) andnon-hydrocarbon gas sample gas chromatography (GC) (GC not shown) areshown in FIG. 26, Table 7 and Table 1. In FIG. 26 the y-axis 4030represents the detector response in pico-amperes (pA) while the x-axis4031 represents the retention time in minutes. In FIG. 26 peak 4032represents the response for methane, peak 4033 represents the responsefor ethane, peak 4034 represents the response for propane, peak 4035represents the response for butane, peak 4036 represents the responsefor pentane and peak 4037 represents the response for hexane. Resultsfor the liquid collected and analyzed by whole oil gas chromatography(WOGC) are shown in FIG. 27, Table 8 and Table 1. In FIG. 27 the y-axis6000 represents the detector response in pico-amperes (pA) while thex-axis 6001 represents the retention time in minutes. The GCchromatogram is shown generally by label 6002 with individual identifiedpeaks labeled with abbreviations.

TABLE 7 Peak and area details for FIG. 26 - Example 4 - 1000 psistress - gas GC Peak RetTime Area Number [min] [pA*s] Name 1 0.9101.43817e4 Methane 2 1.000 301.69287 ? 3 1.078 1.37821e4 Ethane 4 2.5411.64047e4 Propane 5 4.249 2286.08032 iC4 6 4.924 992.04395 ? 7 5.0306167.50000 n-Butane 8 5.303 534.37000 ? 9 5.583 358.96567 ? 10 6.13127.44937 ? 11 6.376 1174.68872 iC5 12 6.740 223.61662 ? 13 6.9022340.79248 n-Pentane 14 7.071 5.29245 ? 15 7.136 309.94775 ? 16 7.295154.59171 ? 17 7.381 169.53279 ? 18 7.555 2.80458 ? 19 7.601 5.22327 ?20 7.751 117.69164 ? 21 8.134 29.41086 ? 22 8.219 19.39338 ? 23 8.342133.52739 ? 24 8.492 281.61343 2-methyl pentane 25 8.647 22.19704 ? 268.882 99.56919 ? 27 9.190 86.65676 ? 28 9.443 657.28754 n-Hexane 299.552 4.12572 ? 30 9.646 34.33701 ? 31 9.710 59.12064 ? 32 9.78862.97972 ? 33 9.847 15.13559 ? 34 9.909 6.88310 ? 35 10.009 29.11555 ?36 10.223 23.65434 ? 37 10.298 173.95422 ? 38 10.416 3.37255 ? 39 10.5697.64592 ? 40 11.246 47.30062 ? 41 11.485 32.04262 ? 42 11.560 13.74583 ?43 11.702 2.68917 ? 44 11.815 36.51670 ? 45 11.941 6.45255 ? 46 12.10328.44484 ? 47 12.172 5.96475 ? 48 12.304 17.59856 ? 49 12.399 15.17446 ?50 12.490 31.96492 ? 51 12.584 3.27834 ? 52 12.675 14.08259 ? 53 12.934207.21574 ? 54 13.105 8.29743 ? 55 13.151 2.25476 ? 56 13.201 8.36965 ?57 13.312 9.49917 ? 58 13.436 6.09893 ? 59 13.521 46.34579 ? 60 13.90020.53506 ? 61 14.090 8.41120 ? 62 14.318 4.36870 ? 63 14.550 8.68951 ?64 14.610 4.39150 ? 65 14.727 4.35713 ? 66 14.870 37.17881 ? 67 14.9515.78219 ? 68 15.080 5.54470 ? 69 15.136 8.07308 ? 70 15.336 2.07075 ? 7115.425 2.67118 ? 72 15.516 8.47004 ? 73 15.569 3.89987 ? 74 15.6413.96979 ? 75 15.776 40.75155 ? 76 16.558 5.06379 ? 77 16.641 8.43767 ?78 17.437 6.00180 ? 79 18.095 7.66881 ? 80 15.853 3.97375 ? 81 16.0165.68997 ? 82 16.482 3.27234 ?

TABLE 8 Peak and area details from FIG. 27 - Example 4 - 1000 psistress - liquid GC. RetTime Peak Area Compound Peak # [min] [pA*s] Name1 2.737 117.78948 iC4 2 2.901 923.40125 nC4 3 3.528 1079.83325 iC5 43.891 3341.44604 nC5 5 5.493 1364.53186 2MP 6 5.930 533.68530 3MP 76.552 5160.12207 nC6 8 7.452 1770.29932 MCP 9 8.717 487.04718 BZ 109.206 712.61566 CH 11 10.634 7302.51123 nC7 12 11. 1755.92236 MCH 1312.760 2145.57666 TOL 14 14.755 6434.40430 nC8 15 18.503 6007.12891 nC916 21.906 5417.67480 nC10 17 25.030 4565.11084 nC11 18 27.936 3773.91943nC12 19 30.656 3112.23950 nC13 20 33.220 2998.37720 nC14 21 35.6392304.97632 nC15 22 37.927 2197.88892 nC16 23 40.102 1791.11877 nC17 2440.257 278.39423 Pr 25 42.171 1589.64233 nC18 26 42.428 241.65131 Ph 2744.141 1442.51843 nC19 28 46.025 1031.68481 nC20 29 47.825 957.65479nC21 30 49.551 609.59943 nC22 31 51.208 526.53339 nC23 32 52.798383.01022 nC24 33 54.329 325.93640 nC25 34 55.806 248.12935 nC26 3557.230 203.21725 nC27 36 58.603 168.78055 nC28 37 59.934 140.40034 nC2938 61.222 95.47594 nC30 39 62.622 77.49546 nC31 40 64.234 49.08135 nC3241 66.114 33.61663 nC33 42 68.350 27.46170 nC34 43 71.030 35.89277 nC3544 74.162 16.87499 nC36 45 78.055 29.21477 nC37 46 82.653 9.88631 nC38Totals: 7.38198e4

Example 5

Conducted in a manner similar to that of Example 2 on a core specimenfrom oil shale block CM-1B; however, in this example the appliedeffective stress was 1,000 psi. Results for the gas collected andanalyzed by hydrocarbon gas sample gas chromatography (GC) andnon-hydrocarbon gas sample gas chromatography (GC) (GC not shown) areshown in FIG. 28, Table 9 and Table 1. In FIG. 28 the y-axis 4040represents the detector response in pico-amperes (pA) while the x-axis4041 represents the retention time in minutes. In FIG. 28 peak 4042represents the response for methane, peak 4043 represents the responsefor ethane, peak 4044 represents the response for propane, peak 4045represents the response for butane, peak 4046 represents the responsefor pentane and peak 4047 represents the response for hexane.

TABLE 9 Peak and area details for FIG. 28 - Example 5 - 1000 psistress - gas GC Peak RetTime Area Number [min] [pA*s] Name 1 0.9101.59035e4 Methane 2 0.999 434.21375 ? 3 1.077 1.53391e4 Ethane 4 2.5371.86530e4 Propane 5 4.235 2545.45850 iC4 6 4.907 1192.68970 ? 7 5.0156814.44678 n-Butane 8 5.285 687.83679 ? 9 5.564 463.25885 ? 10 6.10630.02624 ? 11 6.351 1295.13477 iC5 12 6.712 245.26985 ? 13 6.8762561.11792 n-Pentane 14 7.039 4.50998 ? 15 7.109 408.32999 ? 16 7.268204.45311 ? 17 7.354 207.92183 ? 18 7.527 4.02397 ? 19 7.574 5.65699 ?20 7.755 2.35952 ? 21 7.818 2.00382 ? 22 8.107 38.23093 ? 23 8.19320.54333 ? 24 8.317 148.54445 ? 25 8.468 300.31586 2-methyl pentane 268.622 26.06131 ? 27 8.858 113.70123 ? 28 9.168 90.37163 ? 29 9.422694.74438 n-Hexane 30 9.531 4.88323 ? 31 9.625 45.91505 ? 32 9.68976.32931 ? 33 9.767 77.63214 ? 34 9.826 19.23768 ? 35 9.889 8.54605 ? 369.989 37.74959 ? 37 10.204 30.83943 ? 38 10.280 184.58420 ? 39 10.3974.43609 ? 40 10.551 10.59880 ? 41 10.843 2.30370 ? 42 11.231 55.64666 ?43 11.472 35.46931 ? 44 11.547 17.16440 ? 45 11.691 3.30460 ? 46 11.80439.46368 ? 47 11.931 7.32969 ? 48 12.094 30.59748 ? 49 12.163 6.93754 ?50 12.295 18.69523 ? 51 12.391 15.96837 ? 52 12.482 33.66422 ? 53 12.5772.02121 ? 54 12.618 2.32440 ? 55 12.670 12.83803 ? 56 12.851 2.22731 ?57 12.929 218.23195 ? 58 13.100 14.33166 ? 59 13.198 10.20244 ? 6013.310 12.02551 ? 61 13.432 8.23884 ? 62 13.519 47.64641 ? 63 13.89822.63760 ? 64 14.090 9.29738 ? 65 14.319 3.88012 ? 66 14.551 9.26884 ?67 14.612 4.34914 ? 68 14.729 4.07543 ? 69 14.872 46.24465 ? 70 14.9546.62461 ? 71 15.084 3.92423 ? 72 15.139 8.60328 ? 73 15.340 2.17899 ? 7415.430 2.96646 ? 75 15.521 9.66407 ? 76 15.578 4.27190 ? 77 15.6454.37904 ? 78 15.703 2.68909 ? 79 15.782 46.97895 ? 80 15.859 4.69475 ?81 16.022 7.36509 ? 82 16.489 3.91073 ? 83 16.564 6.22445 ? 84 16.64810.24660 ? 85 17.269 2.69753 ? 86 17.445 10.16989 ? 87 17.925 2.28341 ?88 17.979 2.71101 ? 89 18.104 11.19730 ?

TABLE 1 Summary data for Examples 1-5. Example 1 Example 2 Example 3Example 4 Example 5 Effective Stress (psi) 0 400 400 1000 1000 Sampleweight (g) 82.46 42.57 48.34 43.61 43.73 Sample weight loss (g) 19.2110.29 11.41 10.20 9.17 Fluids Recovered: Oil (g) 10.91 3.63 3.77 3.022.10 36.2 gal/ton 23.4 gal/ton 21.0 gal/ton 19.3 gal/ton 13/1 gal/tonWater (g) 0.90 0.30 0.34 0.39 0.28 2.6 gal/ton 1.7 gal/ton 1.7 gal/ton2.1 gal/ton 1.5 gal/ton HC gas (g) 2.09 1.33 1.58 1.53 1.66 683 scf/ton811 scf/ton 862 scf/ton 905 scf/ton 974 scf/ton CO₂ (g) 3.35 1.70 1.641.74 1.71 700 scf/ton 690 scf/ton 586 scf/ton 690 scf/ton 673 scf/tonH₂S (g) 0.06 0.0 0.0 0.0 0.0 Coke Recovered: 0.0 0.73 0.79 .47 0.53Inferred Oil (g) 0.0 1.67 1.81 1.07 1.21 0 gal/ton 10.8 gal/ton 10.0gal/ton 6.8 gal/ton 7.6 gal/ton Total Oil (g) 10.91 5.31 5.58 4.09 3.3036.2 gal/ton 34.1 gal/ton 31.0 gal/ton 26.1 gal/ton 20.7 gal/ton Balance(g) 1.91 2.59 3.29 3.05 2.91

Heating experiments were conducted on several additional oil shalespecimens and the liquids and gases released from the heated oil shaleexamined in detail. An oil shale sample from the Mahogany formation inthe Uinta Basin in Utah was collected. A solid, continuous block of theoil shale formation, approximately 0.5 cubic foot in size, was collectedfrom Hell's Hole Canyon in Utah. The oil shale block was designatedHHC-2. The core specimens taken from this block, as described in thefollowing examples, were all taken from the same stratigraphic interval.The heating tests were conducted using a Parr vessel, model number243HC5, which is shown in FIG. 18 and is available from Parr InstrumentCompany.

Example 6

Oil shale block HHC-2 was sampled across the bedding planes to producesamples with an approximately uniform distribution of laminae that wereused in four zero effective stress experiments (Examples 6, 7, 13 & 14).This example describes the experimental methodology common to theseexperiments with individual details for each experiment summarized inTable 15.

For each unstressed experiment, a screen 7000 served as a support foreach specimen 7001 (FIG. 17). The oil shale core specimen 7001, wasplaced on the screen and the entire assembly placed into a Parr heatingvessel. The mass of each sample is indicated in Table 15. The Parrvessel 7010, shown in FIG. 18, has an internal volume of 565milliliters. Argon was used to flush the Parr vessel 7010 several timesto remove air present in the chamber and the vessel was then pressurizedto 50, 200, or 500 psi with argon (see Table 15). After the vessel waspressurized its mass was determined and recorded. The Parr vessel wasthen placed in a furnace that was designed to fit the Parr vessel. Thefurnace was initially at room temperature and was heated to either 375or 393° C. (see Table 15) after the Parr vessel was placed in it. TheParr vessel achieved the desired experimental temperature after about 3hours and remained at that temperature for 24 hours. The Parr vessel wasthen removed from the furnace and allowed to cool to room temperatureover a period of approximately 16 hours. Once the vessel reached roomtemperature its mass was determined and recorded. No measurable mass waslost or gained in any experiment described herein.

The room temperature Parr vessel was sampled to obtain a representativeportion of the gas remaining in the vessel following the heatingexperiment. A gas sampling cylinder 150 milliliters in volume wasevacuated, attached to the Parr vessel and the pressure allowed toequilibrate. The Parr vessel was then vented, to achieve atmosphericpressure, opened, and liquid collected from the bottom of the Parrvessel. Water was separated from the hydrocarbon layer and weighed. Theamount collected is noted in Table 15. The collected hydrocarbon liquidswere placed in a small vial, sealed and stored in the absence of lightat a constant temperature of 7° C. The solid core specimen was weighedand its new mass recorded (see Table 15). All samples lost mass as aresult of heating. C4-C19 liquid sample gas-chromatography (C4-C19 GC)testing of the liquid yielded the results shown in FIGS. 39-52, andTable 16 while liquid chromatography (LC) followed by gaschromatography/mass spectrometry (GC/MS) analysis for such samples isdiscussed with reference to FIGS. 53-59 and later herein. The C4-C19 GCchromatograms are shown and are generally label as discussed below withindividual identified peaks labeled with abbreviations.

Example 8

Oil shale block HHC-2 described in Example 6 was cored perpendicular tobedding to yield a 1 inch diameter cores for use in experimentssubjected to effective stress conditions. With reference to FIG. 21, thecore specimens 7050 were approximately 2 inches in length with the massof each sample indicated in Table 15. The following details theexperimental procedures for the stressed experiments of Examples 8-12, &15-19 insofar as they differed from the unstressed experiments describedfor Example 6.

The core specimens 7050 were then placed in Berea sandstone cylinders7051 with a 1-inch inner diameter and a 1.39 inch outer diameter. Bereaplugs 7052 and 7053 were placed at each end of this assembly, so thatthe core specimens were completely surrounded by Berea. The Bereacylinders and plugs were fired at 500° C. for two hours prior to usewith the mini load frame. The Berea cylinder 7051 along with the corespecimen 7050 and the Berea end plugs 7052 and 7053 were placed in aslotted stainless steel sleeve and clamped into place. The sampleassembly 7060 was placed in a spring-loaded mini-load-frame 7061 asshown in FIG. 22. Load was applied by tightening the nuts 7062 and 7063at the top of the load frame 7061 to compress the springs 7064 and 7065.The springs 7064 and 7065 were high temperature, Inconel springs, whichdelivered either 400 or 1000 psi effective stress to the oil shalespecimen 7060 when compressed. Sufficient travel of the springs 7064 and7065 remained in order to accommodate any expansion of the core specimen7060 during the course of heating. In order to ensure that this was thecase, gold foil 7066 was placed on one of the legs of the apparatus togauge the extent of travel. The entire spring loaded apparatus 7061 wasplaced in the Parr vessel (FIG. 18) and the heating experiment conductedas described in Example 6.

As described in Example 6, the room temperature Parr vessel was thensampled to obtain a representative portion of the gas remaining in thevessel following the heating experiment. At this point, the Parr vesselwas vented to achieve atmospheric pressure, the vessel opened, andliquids collected from inside the Parr vessel. Water was separated fromthe hydrocarbon layer and weighed. The amount collected is noted inTable 15. The collected hydrocarbon liquids were placed in a small vial,sealed and stored in the absence of light at a constant temperature of7° C. C4-C19 liquid sample gas-chromatography (C4-C19 GC) testing of theliquid yielded the results shown in FIGS. 39-52, and Table 16 whileliquid chromatography (LC) followed by gas chromatography/massspectrometry (GC/MS) analysis for such samples is discussed withreference to FIGS. 53-59 and later herein. Any additional liquid coatingthe surface of the apparatus or sides of the Parr vessel was collectedwith a paper towel and the weight of this collected liquid added to thetotal liquid collected.

TABLE 15 Summary data for Examples 6-19. Initial Eff. Wt. wipe ExampleAr P Wt. (g) Stress loss Oil Water down Number TC psi (gms) psi (gms)(gms) (gms) (gms) 6 375 500 95.2761 0 11.43 5.17 0.63 0.78 7 375 20066.8161 0 9.78 5.71 0.51 0.41 8 375 500 45.1197 400 6.15 2.27 0.32 0.789 375 200 47.7778 400 6.27 2.44 0.39 0.97 10 375 50 48.3162 400 6.312.88 0.45 0.48 11 375 500 44.6242 1000 6.58 2.08 0.35 0.93 12 375 20048.201 1000 6.86 2.56 0.43 0.76 13 393 500 85.6623 0 15.06 8.25 0.690.17 14 393 200 67.4904 0 11.87 6.60 0.43 0.30 15 393 500 45.3920 4008.73 3.67 0.38 0.35 16 393 200 48.164 400 8.35 3.15 0.32 0.81 17 393 5048.9843 400 8.31 3.19 0.49 0.52 18 393 500 44.7570 1000 8.50 2.50 0.320.59 19 393 200 47.436 1000 8.26 2.11 0.13 0.98

Example 20

This procedure describes the extraction method used to obtain solubleorganic matter (bitumen) from the oil shale sample of Example 20 whichwas subsequently analyzed by the liquid chromatography (LC) followed bygas chromatography/mass spectrometry (GC/MS) procedures discussed laterherein and discussed with reference to FIGS. 53-59.

Extraction Method: The Extraction procedure utilized the laboratoryequipment and chemicals described in Table 17 as well as other typicallaboratory supplies and equipment.

TABLE 17 No. Lab Requirements 1 Soxtec Tecator System (PERSTORPAnalytical) 2 Methylene Chloride (Fisher Optima grade equivalent orbetter) 3 Methanol (Fisher Optima grade equivalent or better) 4Cellulose thimbles (26 mm × 60 mm; Fisher Scientific) 5 Thimble adapters(Perstorp Analytical) 6 Glass extraction cups (small; PerstorpAnalytical) 7 Nitrogen gas (UHP) (Air Liquide) 8 Retsch Mill(micronizer; Brinkman) 9 Retsch Crusher (Lemaire Instruments)

Sample preparation: The Retsch mill and crusher were thoroughly cleanedand the sample was micronized to a particle size of 0.5 micron. About 30grams of the micronized sample was weighed in the thimble to be used inthe extraction.

Extraction procedure: Table 18 describes the extraction method.

TABLE 18 Step Action 1 Wash the Soxtec Tecator extraction system andclean the Teflon O-ring seals with methylene chloride. 2 Run a methylenechloride/methanol (9:1) blank through the system. 3 Place a clean TeflonO-ring seal into the groove at the bottom of condenser. 4 Turn onrefrigerated bath/circulators and check flow. 5 Set the hot oil bath at120° C. 6 Insert the thimble (with sample inside) into the condenser byfastening the thimble adapter to the condenser rod. 7 Place 2 glassbeads and 50 mls (for small extraction cups) of Methylene Chloride:Methanol solution (9:1) in glass extraction cups. 8 Place the extractioncups on the Tecator system. 9 Bring solvent to a boil, lower thimbleinto solvent and extract as follows: 1. Extract 1 hour with thimble inextraction cup. 2. Rinse 1 hour with thimble above extraction cup. 3.Close stop cocks for faster evaporation. 4. Evaporate down toapproximately 10 mls. 10 Remove extraction cups from Tecator System. 11Transfer the extract to the pre-weighed 20 mls vial and bring toconstant weight at 40° C. under nitrogen.

Quality Control:

To ensure reproducible results, a known sediment standard was maintainedas the QC extraction standard and was tested in conjunction with thesample. The extraction yield for the standard was within the acceptable2 standard deviation range.

Core Plugs

Heating experiments on oil shale at 375 deg. C. under stressed andunstressed conditions confirm that porosity is enhanced by the kerogenconversion process. Exemplary core plugs are provided in FIGS. 62, 64and 66. An unheated oil shale core plug 620 is depicted in FIG. 62. Anunheated thin section 621 from the core plug 620 is shown in FIG. 63with a scale reference marker 622 denoting a size of 500 μm. Note thelack of porosity in the thin section 621. The thin section 621 isdominated by organic matter mixed with a matrix of clay and calcitedolomite. The larger white specs are quartz grains (rounded) or calciterhombs. FIG. 64 depicts a core plug 630 that has been heated to 375° C.in a Parr vessel in an inert argon atmosphere with no simulatedlithostatic stress applied. The plug 630 shows ample evidence ofsplitting along laminae presumably where organic material was mostabundant. The thin section 631 depicted in FIG. 65 shows a network oflarge pores and cracks 632. FIG. 65 also includes a scale referencemarker 633 denoting a size of 500 μm. Both the plug 630 and the thinsection 631 exhibit the swelling associated with kerogen conversion andthe resultant porous network developed. FIG. 66 depicts an oil shaleplug 643 placed in a sleeve 641 and end caps 642 a & 642 b of sandstone.The jacketed core 640 was placed in a spring-loaded mini-load-frameassembly (not shown) to simulate overburden stresses of up to 1,000 psi,and then heated to 375° C. The plug photograph depicted in FIG. 66 is aslice through a heated oil shale plug 643 inside its sandstone sleeve641 and end caps 642 a & 642 b. Note the lack of expansion cracks andthe preservation of lamination. In the thin section 644 depicted in FIG.67 small fractures 645 that occur in clusters within the oil shale canbe observed. These fractures 645 are only 50-100 microns wide. FIG. 67also includes a scale reference marker 646 denoting a size of 500 μm.Some fractures 645 are oriented parallel to lamination while others areoriented at various angles to lamination. In addition to the fractures,the groundmass of the oil shale contains numerous small pores that forma microporous network. These pores and microfractures are <50 microns insize. Thus kerogen conversion still takes place and porosity is createdwithin the oil shale converted under stress but with a less substantialvolume expansion. This set of experiments clearly indicates that evenunder overburden stress conditions, the kerogen conversion and expulsionprocess creates porosity and presumably, permeability that was notpresent in the original oil shale.

Analysis

The gas and liquid samples obtained through the experimental proceduresand gas and liquid sample collection procedures described for Examples1-5, were analyzed by the following hydrocarbon gas sample gaschromatography (GC) analysis methodology, non-hydrocarbon gas sample gaschromatography (GC) analysis methodology, gas sample GC peakidentification and integration methodology, whole oil gas chromatography(WOGC) analysis methodology, and whole oil gas chromatography (WOGC)peak identification and integration methodology.

Gas samples collected during the heating tests as described in Examples1-5 were analyzed for both hydrocarbon and non-hydrocarbon gases, usingan Agilent Model 6890 Gas Chromatograph coupled to an Agilent Model 5973quadrapole mass selective detector. The 6890GC was configured with twoinlets (front and back) and two detectors (front and back) with twofixed volume sample loops for sample introduction. Peak identificationsand integrations were performed using the Chemstation software (RevisionA.03.01) supplied with the GC instrument. For hydrocarbon gases, the GCconfiguration consisted of the following:

-   -   a) split/splitless inlet (back position of the GC)    -   b) FID (Flame ionization detector) back position of the GC    -   c) HP Ultra-2 (5% Phenyl Methyl Siloxane) capillary columns        (two) (25 meters×200 μm ID) one directed to the FID detector,        the other to an Agilent 5973 Mass Selective Detector    -   d) 500 μl fixed volume sample loop    -   e) six-port gas sampling valve    -   f) cryogenic (liquid nitrogen) oven cooling capability    -   g) Oven program −80° C. for 2 mins., 20° C./min. to 0° C., then        4° C./min to 20° C., then 10° C./min. to 100° C., hold for 1        min.    -   h) Helium carrier gas flow rate of 2.2 ml/min    -   i) Inlet temperature 100° C.    -   j) Inlet pressure 19.35 psi    -   k) Split ratio 25:1    -   l) FID temperature 310° C.

For non-hydrocarbon gases (e.g., argon, carbon dioxide and hydrogensulfide) the GC configuration consisted of the following:

-   -   a) PTV (programmable temperature vaporization) inlet (front        position of the GC)    -   b) TCD (Thermal conductivity detector) front position of the GC    -   c) GS-GasPro capillary column (30 meters×0.32 mm ID)    -   d) 100 μl fixed volume sample loop    -   e) six port gas sampling valve    -   f) Oven program: 25° C. hold for 2 min., then 10° C./min to 200°        C., hold 1 min.    -   g) Helium carrier gas flow rate of 4.1 ml/min.    -   h) Inlet temperature 200° C.    -   i) Inlet pressure 14.9 psi    -   j) Splitless mode    -   k) TCD temperature 250° C.

For Examples 1-5, a stainless steel sample cylinder containing gascollected from the Parr vessel (FIG. 18) was fitted with a two stage gasregulator (designed for lecture bottle use) to reduce gas pressure toapproximately twenty pounds per square inch. A septum fitting waspositioned at the outlet port of the regulator to allow withdrawal ofgas by means of a Hamilton model 1005 gas-tight syringe. Both the septumfitting and the syringe were purged with gas from the stainless steelsample cylinder to ensure that a representative gas sample wascollected. The gas sample was then transferred to a stainless steel cell(septum cell) equipped with a pressure transducer and a septum fitting.The septum cell was connected to the fixed volume sample loop mounted onthe GC by stainless steel capillary tubing. The septum cell and sampleloop were evacuated for approximately 5 minutes. The evacuated septumcell was then isolated from the evacuated sample loop by closure of aneedle valve positioned at the outlet of the septum cell. The gas samplewas introduced into the septum cell from the gas-tight syringe throughthe septum fitting and a pressure recorded. The evacuated sample loopwas then opened to the pressurized septum cell and the gas sampleallowed to equilibrate between the sample loop and the septum cell forone minute. The equilibrium pressure was then recorded, to allowcalculation of the total moles of gas present in the sample loop beforeinjection into the GC inlet. The sample loop contents were then sweptinto the inlet by Helium carrier gas and components separated byretention time in the capillary column, based upon the GC oventemperature program and carrier gas flow rates.

Calibration curves, correlating integrated peak areas withconcentration, were generated for quantification of gas compositionsusing certified gas standards. For hydrocarbon gases, standardscontaining a mixture of methane, ethane, propane, butane, pentane andhexane in a helium matrix in varying concentrations (parts per million,mole basis) were injected into the GC through the fixed volume sampleloop at atmospheric pressure. For non-hydrocarbon gases, standardscontaining individual components, i.e., carbon dioxide in helium andhydrogen sulfide in natural gas, were injected into the GC at varyingpressures in the sample loop to generate calibration curves.

The hydrocarbon gas sample molar percentages reported in FIG. 16 wereobtained using the following procedure. Gas standards for methane,ethane, propane, butane, pentane and hexane of at least three varyingconcentrations were run on the gas chromatograph to obtain peak arearesponses for such standard concentrations. The known concentrationswere then correlated to the respective peak area responses within theChemstation software to generate calibration curves for methane, ethane,propane, butane, pentane and hexane. The calibration curves were plottedin Chemstation to ensure good linearity (R2>0.98) between concentrationand peak intensity. A linear fit was used for each calibrated compound,so that the response factor between peak area and molar concentrationwas a function of the slope of the line as determined by the Chemstationsoftware. The Chemstation software program then determined a responsefactor relating GC peak area intensity to the amount of moles for eachcalibrated compound. The software then determined the number of moles ofeach calibrated compound from the response factor and the peak area. Thepeak areas used in Examples 1-5 are reported in Tables 2, 4, 5, 7, and9. The number of moles of each identified compound for which acalibration curve was not determined (i.e., iso-butane, iso-pentane, and2-methyl pentane) was then estimated using the response factor for theclosest calibrated compound (i.e., butane for iso-butane; pentane foriso-pentane; and hexane for 2-methyl pentane) multiplied by the ratio ofthe peak area for the identified compound for which a calibration curvewas not determined to the peak area of the calibrated compound. Thevalues reported in FIG. 16 were then taken as a percentage of the totalof all identified hydrocarbon gas GC areas (i.e., methane, ethane,propane, iso-butane, n-butane, iso-pentane, n-pentane, 2-methyl pentane,and n-hexane) and calculated molar concentrations. Thus the graphedmethane to normal C6 molar percentages for all of the experiments do notinclude the molar contribution of the unidentified hydrocarbon gasspecies listed in Tables 2, 4, 5, 7, or 9 (e.g., peak numbers 2, 6,8-11, 13, 15-22, 24-26, and 28-78 in Table 2).

Liquid samples collected during the heating tests as described inExamples 1, 3 and 4 were analyzed by whole oil gas chromatography (WOGC)according to the following procedure. Samples, QA/QC standards andblanks (carbon disulfide) were analyzed using an Ultra 1 Methyl Siloxanecolumn (25 m length, 0.32 μm diameter, 0.52 μm film thickness) in anAgilent 6890 GC equipped with a split/splitless injector, autosamplerand flame ionization detector (FID). Samples were injected onto thecapillary column in split mode with a split ratio of 80:1. The GC oventemperature was kept constant at 20° C. for 5 min, programmed from 20°C. to 300° C. at a rate of 5° C. min⁻¹, and then maintained at 300° C.for 30 min (total run time=90 min.). The injector temperature wasmaintained at 300° C. and the FID temperature set at 310° C. Helium wasused as carrier gas at a flow of 2.1 mL min⁻¹. Peak identifications andintegrations were performed using Chemstation software Rev.A.10.02[1757] (Agilent Tech. 1990-2003) supplied with the Agilent instrument.

Standard mixtures of hydrocarbons were analyzed in parallel by the WOGCmethod described above and by an Agilent 6890 GC equipped with asplit/splitless injector, autosampler and mass selective detector (MS)under the same conditions. Identification of the hydrocarbon compoundswas conducted by analysis of the mass spectrum of each peak from theGC-MS. Since conditions were identical for both instruments, peakidentification conducted on the GC-MS could be transferred to the peaksobtained on the GC-FID. Using these data, a compound table relatingretention time and peak identification was set up in the GC-FIDChemstation. This table was used for peak identification.

The gas chromatograms obtained on the liquid samples (FIGS. 4, 9 and 11)were integrated using a pseudo-component technique. The convention usedfor identifying each pseudo-component was to integrate all contributionsfrom normal alkane to next occurring normal alkane with thepseudo-component being named by the late eluting n-alkane. For example,the C-10 pseudo-component would be obtained from integration beginningjust past normal-C9 and continue just through normal-C10. The carbonnumber weight % and mole % values for the pseudo-components obtained inthis manner were assigned using correlations developed by Katz andFiroozabadi (Katz, D. L., and A. Firoozabadi, 1978. Predicting phasebehavior of condensate/crude-oil systems using methane interactioncoefficients, J. Petroleum Technology (November 1978), 1649-1655).Results of the pseudo-component analyses for Examples 1, 3 and 4 areshown in Tables 10, 11 and 12.

An exemplary pseudo component weight percent calculation is presentedbelow with reference to Table 10 for the C10 pseudo component forExample 1 in order to illustrate the technique. First, the C-10pseudo-component total area is obtained from integration of the areabeginning just past normal-C9 and continued just through normal-C10 asdescribed above. The total integration area for the C10 pseudo componentis 10551.700 pico-ampere-seconds (pAs). The total C10 pseudo componentintegration area (10551.700 pAs) is then multiplied by the C10 pseudocomponent density (0.7780 g/ml) to yield an “area X density” of 8209.22pAs g/ml. Similarly, the peak integration areas for each pseudocomponent and all lighter listed compounds (i.e., nC3, iC4, nC4, iC5 &nC5) are determined and multiplied by their respective densities toyield “area X density” numbers for each respective pseudo component andlisted compound. The respective determined “area X density” numbers foreach pseudo component and listed compound is then summed to determine a“total area X density” number. The “total area X density” number forExample 1 is 96266.96 pAs g/ml. The C10 pseudo component weightpercentage is then obtained by dividing the C10 pseudo component “area Xdensity” number (8209.22 pAs g/ml) by the “total area X density” number(96266.96 pAs g/ml) to obtain the C10 pseudo component weight percentageof 8.53 weight percent.

An exemplary pseudo component molar percent calculation is presentedbelow with reference to Table 10 for the C10 pseudo component forExample 1 in order to further illustrate the pseudo component technique.First, the C-10 pseudo-component total area is obtained from integrationof the area beginning just past normal-C9 and continued just throughnormal-C10 as described above. The total integration area for the C10pseudo component is 10551.700 pico-ampere-seconds (pAs). The total C10pseudo component integration area (10551.700 pAs) is then multiplied bythe C10 pseudo component density (0.7780 g/ml) to yield an “area Xdensity” of 8209.22 pAs g/ml. Similarly, the integration areas for eachpseudo component and all lighter listed compounds (i.e., nC3, iC4, nC4,iC5 & nC5) are determined and multiplied by their respective densitiesto yield “area X density” numbers for each respective pseudo componentand listed compound. The C10 pseudo component “area X density” number(8209.22 pAs g/ml) is then divided by the C10 pseudo component molecularweight (134.00 g/mol) to yield a C10 pseudo component “area Xdensity/molecular weight” number of 61.26 pAs mol/ml. Similarly, the“area X density” number for each pseudo component and listed compound isthen divided by such components or compounds respective molecular weightto yield an “area X density/molecular weight” number for each respectivepseudo component and listed compound. The respective determined “area Xdensity/molecular weight” numbers for each pseudo component and listedcompound is then summed to determine a “total area X density/molecularweight” number. The total “total area X density/molecular weight” numberfor Example 1 is 665.28 pAs mol/ml. The C10 pseudo component molarpercentage is then obtained by dividing the C10 pseudo component “area Xdensity/molecular weight” number (61.26 pAs mol/ml) by the “total area Xdensity/molecular weight” number (665.28 pAs mol/ml) to obtain the C10pseudo component molar percentage of 9.21 molar percent.

TABLE 10 Pseudo-components for Example 1 - GC of liquid - 0 stress Avg.Boiling Density Molecular Component Area (cts.) Area % Pt. (° F.) (g/ml)Wt. (g/mol) Wt. % Mol % nC₃ 41.881 0.03 −43.73 0.5069 44.10 0.02 0.07iC₄ 120.873 0.10 10.94 0.5628 58.12 0.07 0.18 nC₄ 805.690 0.66 31.100.5840 58.12 0.49 1.22 iC₅ 1092.699 0.89 82.13 0.6244 72.15 0.71 1.42nC₅ 2801.815 2.29 96.93 0.6311 72.15 1.84 3.68 Pseudo C₆ 7150.533 5.84147.00 0.6850 84.00 5.09 8.76 Pseudo C₇ 10372.800 8.47 197.50 0.722096.00 7.78 11.73 Pseudo C₈ 11703.500 9.56 242.00 0.7450 107.00 9.0612.25 Pseudo C₉ 11776.200 9.61 288.00 0.7640 121.00 9.35 11.18 PseudoC₁₀ 10551.700 8.61 330.50 0.7780 134.00 8.53 9.21 Pseudo C₁₁ 9274.3337.57 369.00 0.7890 147.00 7.60 7.48 Pseudo C₁₂ 8709.231 7.11 407.000.8000 161.00 7.24 6.50 Pseudo C₁₃ 7494.549 6.12 441.00 0.8110 175.006.31 5.22 Pseudo C₁₄ 6223.394 5.08 475.50 0.8220 190.00 5.31 4.05 PseudoC₁₅ 6000.179 4.90 511.00 0.8320 206.00 5.19 3.64 Pseudo C₁₆ 5345.7914.36 542.00 0.8390 222.00 4.66 3.04 Pseudo C₁₇ 4051.886 3.31 572.000.8470 237.00 3.57 2.18 Pseudo C₁₈ 3398.586 2.77 595.00 0.8520 251.003.01 1.73 Pseudo C₁₉ 2812.101 2.30 617.00 0.8570 263.00 2.50 1.38 PseudoC₂₀ 2304.651 1.88 640.50 0.8620 275.00 2.06 1.09 Pseudo C₂₁ 2038.9251.66 664.00 0.8670 291.00 1.84 0.91 Pseudo C₂₂ 1497.726 1.22 686.000.8720 305.00 1.36 0.64 Pseudo C₂₃ 1173.834 0.96 707.00 0.8770 318.001.07 0.49 Pseudo C₂₄ 822.762 0.67 727.00 0.8810 331.00 0.75 0.33 PseudoC₂₅ 677.938 0.55 747.00 0.8850 345.00 0.62 0.26 Pseudo C₂₆ 532.788 0.43766.00 0.8890 359.00 0.49 0.20 Pseudo C₂₇ 459.465 0.38 784.00 0.8930374.00 0.43 0.16 Pseudo C₂₈ 413.397 0.34 802.00 0.8960 388.00 0.38 0.14Pseudo C₂₉ 522.898 0.43 817.00 0.8990 402.00 0.49 0.18 Pseudo C₃₀336.968 0.28 834.00 0.9020 416.00 0.32 0.11 Pseudo C₃₁ 322.495 0.26850.00 0.9060 430.00 0.30 0.10 Pseudo C₃₂ 175.615 0.14 866.00 0.9090444.00 0.17 0.05 Pseudo C₃₃ 165.912 0.14 881.00 0.9120 458.00 0.16 0.05Pseudo C₃₄ 341.051 0.28 895.00 0.9140 472.00 0.32 0.10 Pseudo C₃₅286.861 0.23 908.00 0.9170 486.00 0.27 0.08 Pseudo C₃₆ 152.814 0.12922.00 0.9190 500.00 0.15 0.04 Pseudo C₃₇ 356.947 0.29 934.00 0.9220514.00 0.34 0.10 Pseudo C₃₈ 173.428 0.14 947.00 0.9240 528.00 0.17 0.05Totals 122484.217 100.00 100.00 100.00

TABLE 11 Pseudo-components for Example 3 - GC of liquid - 400 psi stressAvg. Boiling Density Molecular Wt. Component Area Area % Pt. (° F.)(g/ml) (g/mol) Wt. % Mol % nC₃ 35.845 0.014 −43.730 0.5069 44.10 0.010.03 iC₄ 103.065 0.041 10.940 0.5628 58.12 0.03 0.07 nC₄ 821.863 0.32831.100 0.5840 58.12 0.24 0.62 iC₅ 1187.912 0.474 82.130 0.6244 72.150.37 0.77 nC₅ 3752.655 1.498 96.930 0.6311 72.15 1.20 2.45 Pseudo C₆12040.900 4.805 147.000 0.6850 84.00 4.17 7.34 Pseudo C₇ 20038.600 7.997197.500 0.7220 96.00 7.31 11.26 Pseudo C₈ 24531.500 9.790 242.000 0.7450107.00 9.23 12.76 Pseudo C₉ 25315.000 10.103 288.000 0.7640 121.00 9.7711.94 Pseudo C₁₀ 22640.400 9.035 330.500 0.7780 134.00 8.90 9.82 PseudoC₁₁ 20268.100 8.089 369.000 0.7890 147.00 8.08 8.13 Pseudo C₁₂ 18675.6007.453 407.000 0.8000 161.00 7.55 6.93 Pseudo C₁₃ 16591.100 6.621 441.0000.8110 175.00 6.80 5.74 Pseudo C₁₄ 13654.000 5.449 475.500 0.8220 190.005.67 4.41 Pseudo C₁₅ 13006.300 5.191 511.000 0.8320 206.00 5.47 3.92Pseudo C₁₆ 11962.200 4.774 542.000 0.8390 222.00 5.07 3.38 Pseudo C₁₇8851.622 3.533 572.000 0.8470 237.00 3.79 2.36 Pseudo C₁₈ 7251.438 2.894595.000 0.8520 251.00 3.12 1.84 Pseudo C₁₉ 5946.166 2.373 617.000 0.8570263.00 2.57 1.45 Pseudo C₂₀ 4645.178 1.854 640.500 0.8620 275.00 2.021.09 Pseudo C₂₁ 4188.168 1.671 664.000 0.8670 291.00 1.83 0.93 PseudoC₂₂ 2868.636 1.145 686.000 0.8720 305.00 1.26 0.61 Pseudo C₂₃ 2188.8950.874 707.000 0.8770 318.00 0.97 0.45 Pseudo C₂₄ 1466.162 0.585 727.0000.8810 331.00 0.65 0.29 Pseudo C₂₅ 1181.133 0.471 747.000 0.8850 345.000.53 0.23 Pseudo C₂₆ 875.812 0.350 766.000 0.8890 359.00 0.39 0.16Pseudo C₂₇ 617.103 0.246 784.000 0.8930 374.00 0.28 0.11 Pseudo C₂₈538.147 0.215 802.000 0.8960 388.00 0.24 0.09 Pseudo C₂₉ 659.027 0.263817.000 0.8990 402.00 0.30 0.11 Pseudo C₃₀ 1013.942 0.405 834.000 0.9020416.00 0.46 0.16 Pseudo C₃₁ 761.259 0.304 850.000 0.9060 430.00 0.350.12 Pseudo C₃₂ 416.031 0.166 866.000 0.9090 444.00 0.19 0.06 Pseudo C₃₃231.207 0.092 881.000 0.9120 458.00 0.11 0.03 Pseudo C₃₄ 566.926 0.226895.000 0.9140 472.00 0.26 0.08 Pseudo C₃₅ 426.697 0.170 908.000 0.9170486.00 0.20 0.06 Pseudo C₃₆ 191.626 0.076 922.000 0.9190 500.00 0.090.03 Pseudo C₃₇ 778.713 0.311 934.000 0.9220 514.00 0.36 0.10 Pseudo C₃₈285.217 0.114 947.000 0.9240 528.00 0.13 0.04 Totals 250574.144 100.000100.00 100.00

TABLE 12 Pseudo-components for Example 4 - GC of liquid - 1000 psistress Avg. Boiling Density Molecular Wt. Component Area Area % Pt. (°F.) (g/ml) (g/mol) Wt. % Mol % nC₃ 44.761 0.023 −43.730 0.5069 44.100.01 0.05 iC₄ 117.876 0.060 10.940 0.5628 58.12 0.04 0.11 nC₄ 927.8660.472 31.100 0.5840 58.12 0.35 0.87 iC₅ 1082.570 0.550 82.130 0.624472.15 0.44 0.88 nC₅ 3346.533 1.701 96.930 0.6311 72.15 1.37 2.74 PseudoC₆ 9579.443 4.870 147.000 0.6850 84.00 4.24 7.31 Pseudo C₇ 16046.2008.158 197.500 0.7220 96.00 7.49 11.29 Pseudo C₈ 19693.300 10.012 242.0000.7450 107.00 9.48 12.83 Pseudo C₉ 20326.300 10.334 288.000 0.7640121.00 10.04 12.01 Pseudo C₁₀ 18297.600 9.302 330.500 0.7780 134.00 9.209.94 Pseudo C₁₁ 16385.600 8.330 369.000 0.7890 147.00 8.36 8.23 PseudoC₁₂ 15349.000 7.803 407.000 0.8000 161.00 7.94 7.14 Pseudo C₁₃ 13116.5006.668 441.000 0.8110 175.00 6.88 5.69 Pseudo C₁₄ 10816.100 5.499 475.5000.8220 190.00 5.75 4.38 Pseudo C₁₅ 10276.900 5.225 511.000 0.8320 206.005.53 3.88 Pseudo C₁₆ 9537.818 4.849 542.000 0.8390 222.00 5.17 3.37Pseudo C₁₇ 6930.611 3.523 572.000 0.8470 237.00 3.79 2.32 Pseudo C₁₈5549.802 2.821 595.000 0.8520 251.00 3.06 1.76 Pseudo C₁₉ 4440.457 2.257617.000 0.8570 263.00 2.46 1.35 Pseudo C₂₀ 3451.250 1.755 640.500 0.8620275.00 1.92 1.01 Pseudo C₂₁ 3133.251 1.593 664.000 0.8670 291.00 1.760.87 Pseudo C₂₂ 2088.036 1.062 686.000 0.8720 305.00 1.18 0.56 PseudoC₂₃ 1519.460 0.772 707.000 0.8770 318.00 0.86 0.39 Pseudo C₂₄ 907.4730.461 727.000 0.8810 331.00 0.52 0.23 Pseudo C₂₅ 683.205 0.347 747.0000.8850 345.00 0.39 0.16 Pseudo C₂₆ 493.413 0.251 766.000 0.8890 359.000.28 0.11 Pseudo C₂₇ 326.831 0.166 784.000 0.8930 374.00 0.19 0.07Pseudo C₂₈ 272.527 0.139 802.000 0.8960 388.00 0.16 0.06 Pseudo C₂₉291.862 0.148 817.000 0.8990 402.00 0.17 0.06 Pseudo C₃₀ 462.840 0.235834.000 0.9020 416.00 0.27 0.09 Pseudo C₃₁ 352.886 0.179 850.000 0.9060430.00 0.21 0.07 Pseudo C₃₂ 168.635 0.086 866.000 0.9090 444.00 0.100.03 Pseudo C₃₃ 67.575 0.034 881.000 0.9120 458.00 0.04 0.01 Pseudo C₃₄95.207 0.048 895.000 0.9140 472.00 0.06 0.02 Pseudo C₃₅ 226.660 0.115908.000 0.9170 486.00 0.13 0.04 Pseudo C₃₆ 169.729 0.086 922.000 0.9190500.00 0.10 0.03 Pseudo C₃₇ 80.976 0.041 934.000 0.9220 514.00 0.05 0.01Pseudo C₃₈ 42.940 0.022 947.000 0.9240 528.00 0.03 0.01 Totals196699.994 100.000 100.00 100.00

TOC and Rock-eval tests were performed on specimens from oil shale blockCM-1B taken at the same stratigraphic interval as the specimens testedby the Parr heating method described in Examples 1-5. These testsresulted in a TOC of 21% and a Rock-eval Hydrogen Index of 872 mg/g-toc.

The TOC and rock-eval procedures described below were performed on theoil shale specimens remaining after the Parr heating tests described inExamples 1-5. Results are shown in Table 13.

The Rock-Eval pyrolysis analyses described above were performed usingthe following procedures. Rock-Eval pyrolysis analyses were performed oncalibration rock standards (IFP standard #55000), blanks, and samplesusing a Delsi Rock-Eval II instrument. Rock samples were crushed,micronized, and air-dried before loading into Rock-Eval crucibles.Between 25 and 100 mg of powdered-rock samples were loaded into thecrucibles depending on the total organic carbon (TOC) content of thesample. Two or three blanks were run at the beginning of each day topurge the system and stabilize the temperature. Two or three samples ofIFP calibration standard #55000 with weight of 100+/−1 mg were run tocalibrate the system. If the Rock-Eval T_(max) parameter was 419°C.+/−2° C. on these standards, analyses proceeded with samples. Thestandard was also run before and after every 10 samples to monitor theinstrument's performance.

The Rock-Eval pyrolysis technique involves the rate-programmed heatingof a powdered rock sample to a high temperature in an inert (helium)atmosphere and the characterization of products generated from thethermal breakdown of chemical bonds. After introduction of the samplethe pyrolysis oven was held isothermally at 300° C. for three minutes.Hydrocarbons generated during this stage are detected by aflame-ionization detector (FID) yielding the S₁ peak. The pyrolysis-oventemperature was then increased at a gradient of 25° C./minute up to 550°C., where the oven was held isothermally for one minute. Hydrocarbonsgenerated during this step were detected by the FID and yielded the S₂peak.

Hydrogen Index (HI) is calculated by normalizing the S₂ peak (expressedas mg_(hydrocarbons)/g_(rock)) to weight % TOC (Total Organic Carbondetermined independently) as follows:

HI=(S₂/TOC)*100

where HI is expressed as Mg_(hydrocarbons)/g_(TOC)

Total Organic Carbon (TOC) was determined by well known methods suitablefor geological samples—i.e., any carbonate rock present was removed byacid treatment followed by combustion of the remaining material toproduce and measure organic based carbon in the form of CO2.

TABLE 13 TOC and Rock-eval results on oil shale specimens after the Parrheating tests. Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple5 TOC (%) 12.07 10.83 10.62 11.22 11.63 HI (mg/g-toc) 77 83 81 62 77

The API gravity of Examples 1-5 was estimated by estimating the roomtemperature specific gravity (SG) of the liquids collected and theresults are reported in Table 14. The API gravity was estimated from thedetermined specific gravity by applying the following formula:

API gravity=(141.5/SG)−131.5

The specific gravity of each liquid sample was estimated using thefollowing procedure. An empty 50 μl Hamilton Model 1705 gastight syringewas weighed on a Mettler AE 163 digital balance to determine the emptysyringe weight. The syringe was then loaded by filling the syringe witha volume of liquid. The volume of liquid in the syringe was noted. Theloaded syringe was then weighed. The liquid sample weight was thenestimated by subtracting the loaded syringe measured weight from themeasured empty syringe weight. The specific gravity was then estimatedby dividing the liquid sample weight by the syringe volume occupied bythe liquid sample.

TABLE 14 Estimated API Gravity of liquid samples from Examples 1-5Example Example 1 Example 2 Example 3 Example 4 Example 5 API Gravity29.92 30.00 27.13 32.70 30.00

The liquid samples obtained through the experimental procedures and gasand liquid sample collection procedures described for Examples 6-19,were analyzed by the following hydrocarbon liquid sample C4-C19 gaschromatography (C4-C19 GC) analysis methodology, C4-C19 GC peakidentification and integration methodology. While the liquid samplesfrom Examples 6-19 were also analyzed using the whole oil gaschromatography (WOGC) analysis methodology, and whole oil gaschromatography (WOGC) peak identification and integration methodologydiscussed above with reference to Examples 1-5.

Liquid samples collected during the heating tests described in Examples7-19 were analyzed by a gas chromatographic (GC) procedure designed toproduce well separated GC peaks for materials having carbon numbers inthe range C4-C19. The following procedure describes that analysis.

The gas chromatographic separation was accomplished in two stages—afirst stage to separate the C4-C19 fraction from the sample, discardingthose components present with higher carbon numbers. This C4-C19fraction was then passed to the second stage of GC analysis, where amore complete, analytical separation was accomplished.

The gas chromatography equipment consisted of a Hewlett Packard 5890(Series II) Gas Chromatograph equipped with an FID detector, an HP 6890autosampler, a split injector and a computer supplied with AgilentChemStation software. This GC was augmented with a pre-fractionator asdescribed below.

The first stage of separation, the pre-fractionator, consisted of aninjector port and oven, the oven containing one packed stainless steelcolumn (20% OV101 on 80/100 mesh Chromosorb WHP, ⅛ inch I.D and 4 feetlong), a second packed stainless steel column (5 A mole sieve, 60/80mesh, ⅛ inch ID and 2 feet long), and a multi-port valve. Both the ovenand the injector port were maintained at 300° C. UHP Helium carrier gasflowing at a rate of 25 ml/min was used. The OV101 column was used toisolate the C4-C19 fraction in the sample and the heavier compounds(C19+) were backflushed into the mole sieve column. The multi-port valvewas used in a timed manner to isolate the C4-C19 fraction and providethat fraction as input to the second stage of separation.

The second stage of separation, the analytical separation, consisted ofa split injector, an oven equipped with temperature control, ananalytical column acquired from Agilent (PONA fused silica column 50 min length, 0.2 mm ID and 0.5 μm film thickness) and flame ionizationdetector (FID). The injector and FID detector were maintained at 300° C.

Liquid samples to be analyzed were placed in sealed glass vials suitablefor use in the autosampler and weighed. To each sample 1 μl of 1-hexene(GC grade from Sigma Aldrich) was added. The 1-hexene served as aninternal standard with known amount and also as a retention timestandard. 10 μl of a mixture of additional reference standards was addedto each sample. These reference standards consisted of a mixture ofequal volumes of the following four compounds: 2,3-dimethyl-2-pentene,cis-2-octene, 1-nonene, and 1,2,3,4-tetramethylbenzene. These referencestandards were used as retention time standards.

The autosampler was set to inject 1 μl of sample (containing thestandards). The second stage of separation was accomplished using ahelium flow rate of 1 ml/min and a GC oven temperature program asfollows:

-   -   Initial temp=35° C.    -   Initial hold time=15.00 min    -   Rate 1=1.50° C./min    -   Temp 1_(f)=70° C.    -   Hold Time 1_(f)=0.0 min    -   Rate 2=3.00° C./min    -   Temp 2_(f)=130° C.    -   Hold Time 2_(f)=12.0 min    -   Rate 3=3.00° C./min    -   Temp 3_(f)=300° C.    -   Hold Time 3_(f)=20.0 min        Gas pressure settings on the GC were held at helium=64 psi,        hydrogen=15 psi, and air=44 psi.

Agilent ChemStation Revision A.10.02 software was used to control theinstrument and perform data integration. This software was used to makeany necessary retention time adjustments based on the responses of thestandard materials contained in each sample. Peak assignments were madebased on retention times of known compounds and separate analyses usingGC/mass spectrometry for compound identification.

A quality control sample of a previously collected C4-C19 fraction wasmaintained and run routinely to ensure instrument and datareproducibility.

The C4-C19 GC chromatograms for Examples 6-19 are depicted in FIGS.39-52, with FIG. 39 containing the C4-C19 GC chromatogram for Example 6,FIG. 40 containing the C4-C19 GC chromatogram for Example 7, FIG. 41containing the C4-C19 GC chromatogram for Example 8, FIG. 42 containingthe C4-C19 GC chromatogram for Example 9, FIG. 43 containing the C4-C19GC chromatogram for Example 10, FIG. 44 containing the C4-C19 GCchromatogram for Example 11, FIG. 45 containing the C4-C19 GCchromatogram for Example 12, FIG. 46 containing the C4-C19 GCchromatogram for Example 13, FIG. 47 containing the C4-C19 GCchromatogram for Example 14, FIG. 48 containing the C4-C19 GCchromatogram for Example 15, FIG. 49 containing the C4-C19 GCchromatogram for Example 16, FIG. 50 containing the C4-C19 GCchromatogram for Example 17, FIG. 51 containing the C4-C19 GCchromatogram for Example 18, and FIG. 52 containing the C4-C19 GCchromatogram for Example 19. The y-axis (labeled 450, 455, 460, 465,470, 475, 480, 485, 490, 495, 500, 505, 510 & 515 respectively) of eachof the figures represents signal response in pico-amperes (pA) with thex-axis (labeled 451, 456, 461, 466, 471, 476, 481, 486, 491, 496, 501,506, 511 & 516 respectively) representing retention time in minutes.Each respective chromatogram (labeled 452, 457, 462, 467, 472, 477, 482,487, 492, 497, 502, 507, 512 & 517 respectively), including a series ofpeaks, is identified. Each identified peak for each respectivechromatogram is labeled with abbreviations corresponding to compoundnames.

The C4-C19 GC chromatograms for Examples 6-19 were integrated to obtainindividual peak areas for each identified compound as previouslydiscussed. Some compounds, routinely identified by C4-C19 GC analysis,were not included in the analysis presented here. Compounds whoseconcentrations were sufficiently low that they were found to be belowthe detection limit, as determined by the automated peak integrationtechniques, for one or more of Examples 6-19 are not included in Table16, nor were such compounds included in the calculations used to prepareFIG. 29. A summary of the calculated peak areas for the identified peaksfor each of Examples 6-19 is included in Table 16 below.

In Table 16 below certain common abbreviations are used to denoteparticular compounds or compound elements. For example, “C_” refers tothe carbon number of a referenced compound or portion of a compound asin C5 (pentane), “i” refers to “iso” as in iC5 (isopentane), “M” refersto a “methyl” substituent as in MCyC5 (methyl-cyclopentane), a numberbefore a substituent refers to the position of attachment of thesubstituent as in 2MC6 (2-methyl-cyclohexane), “Cy” refers to “cyclo” asin MCyC6 (methyl-cyclohexane, “n” refers to “normal” as in nC5(normal-pentane), “Bz” refers to benzene, “c” refers to “cis”, “t”refers to “trans”, “D” refers to “di” as in dimethyl (DM), “T” refers to“tri” as in “1_(—)3_(—)5 TMBz” (1,3,5-trimethylbenzene), “E” refers to“ethyl” as in ECyC5 (ethyl-cyclopentane), “Tol” refers to toluene, mXlyand oXly refer to meta-xylene and ortho-xylene respectively, “IP_”refers to an isoprenoid compound with the number denoting the carbonnumber of the particular isoprenoid compound as in IP9, “naph” refers tonaphthalene as in 2MNaph (2-methyl-naphthalene), and “Hexyl” refers to“hexyl” as in HexylCyC6 (hexyl-cyclohexane).

TABLE 16 Identified Compound Peak Areas for Examples 6-19 Ex. 13 Ex. 15Ex. 18 Ex. 8 Ex. 11 Ex. 6 Ex. 9 Compound 393/500/0 393/500/400393/500/1000 375/500/400 375/500/1000 375/500/0 375/200/400 nC3 307012222 9036 1419 4945 11720 4097 iC4 14577 25585 20701 4701 12466 260428750 nC4 61525 91721 81541 14969 41191 67529 25806 iC5 124389 139131133808 47249 81797 120826 57404 nC5 214498 231737 241934 76635 125249153466 89649 2MC5 142240 138317 124548 90777 110559 143375 95052 3MC539883 41951 42934 23859 30630 36964 24672 nC6 174315 169809 186830 89770114925 114891 92728 MCyC5 48600 56782 82829 26109 36572 34286 26678 Bz5862 16631 28651 3893 8554 1504 3860 CyC6 8392 10360 13915 6271 73036676 6233 2MC6 19543 20254 21566 14136 16135 17090 13723 2_3DMC5 103449911 7272 11126 10310 12506 10683 3MC6 43324 42270 37563 34674 3749445301 32482 c1_3DMCyC5 11785 12333 17798 6385 9029 8869 6423 t1_3DMCyC510429 11425 17173 5684 7990 8003 5697 t1_2DMCyC5 17611 19733 25300 1301815606 18074 12433 nC7 116961 112106 117194 83617 92582 93441 80277 MCyC627206 31726 47753 16625 22451 19190 16212 ECyC5 13120 13977 19543 76859785 8999 7439 ctc1_2_4TMCyC5 6964 7626 9562 5324 6119 7467 46252_3_3TMC5 6183 10603 15281 5339 8706 2703 4944 Tol 17401 30634 5761212597 18087 11070 12191 2MC7 70047 66469 54973 67860 67378 78358 638574MC7 17283 16136 11823 15943 15637 19999 15499 3MC7+c1_3DMCyC6 1872421594 28530 14002 17847 17053 13467 1_1DMCyC6 5616 6493 8267 4736 55005376 4467 t1_2DMCyC6 6801 8170 12064 4314 6225 4334 4112 nC8 90517 8587487571 71371 76307 76042 67154 ECyC6 9784 10612 14266 5798 7428 6680 5673IP9 36441 30255 19664 34977 32585 40633 31372 1_1_3TMCyC6 67451 6941871685 76067 73961 83467 71038 EBz 7054 10031 16801 4925 6225 4423 4589mXyl 44614 59863 81247 40493 49280 38201 38910 2_3DMC7 10223 24038 3752915910 12554 14191 14575 3MC8 32855 32181 24051 32724 32243 39088 30359oXyl 14653 22464 36267 10799 14267 10186 10375 nC9 101858 93218 8791282617 84254 88811 77742 Cumene 2901 7520 8888 6625 7935 8184 6224 IP1053783 47941 29598 61657 55678 69422 57218 1E3MBz 15969 20713 33035 1058414374 10348 9902 1E4MBz 21094 25059 34620 19024 21991 19239 180781_3_5TMBz 39623 42681 38619 52422 47097 56611 45270 4MC9 27600 2521716439 30557 28718 35754 28362 2MC9 16654 16866 18834 12978 14080 1503712495 3MC9 13553 11011 5639 20738 15934 20578 20959 1_2_4TMBz 3540545398 60770 31590 37630 30331 29563 nC10 102614 93728 83963 85326 8742092784 79365 1_2_3TMBz 46530 50944 61138 47116 51099 46419 43969 IP1153131 46057 25081 68367 58432 74228 64169 1E3_5DMBz 15979 16506 1814215618 15219 17578 14581 Transdecaline 5321 6465 6992 8362 8321 8239 46595MC10 6122 5529 5244 5863 5778 6337 7966 2MC10 9595 9887 12762 9094 93959644 13853 1E2_3DMBz 7095 7301 9624 6672 7159 6650 6045 nC11 79804 6842658919 66051 66120 71801 62784 2_4DMC10 7737 8199 8477 8504 8164 86965920 Tetralin 3615 4437 5676 3595 3733 3529 3686 5MC11 8535 8847 297410342 9739 11882 9685 2MC11 7526 6953 6077 7395 7263 7990 6461 Naph 25373680 5645 5156 4657 2561 4258 nC12 57116 50173 40697 51047 50557 5551946671 IP13 33496 28236 15869 48783 40194 50238 43477 HexylCyC6 6966 71659944 5000 6271 6893 8069 5MC12 7062 7740 8973 7560 7726 7775 6847 2MC127248 6077 4833 8617 7577 8916 7348 3MC12 8829 8603 10513 7585 8675 78556904 IP14 28729 21527 8594 46307 35283 47416 41223 2MNaph 19500 1880626986 10559 12490 10992 9353 1MNaph 8355 10124 14858 7499 8235 7287 7020nC13 60358 49540 40064 54266 54134 60844 49318 IP15 27770 21873 845248540 36704 47360 42153 DMNaph 11505 13776 17725 8091 9799 8886 7468nC14 58327 48375 37495 51077 51104 56111 44159 1_3&1_7DMNaph 12556 848818800 15493 13072 16007 13716 1_6DMNaph 34937 36280 43517 31086 3368730971 27896 IP16 27618 20675 6337 54276 38608 49543 47297 nC15 5794748654 35978 49985 49673 55976 43505 nC16 53454 41787 29683 45898 4593753132 39257 IP18 17984 12500 4220 38640 26823 35474 32985 nC17 4973239112 26607 47824 45825 54421 41910 Pristane 18861 12675 4990 4825630264 40970 41927 nC18 44093 33861 20379 39946 39340 47957 35325 Phytane9925 6602 2612 24166 15769 21983 21467 nC19 42725 31598 17647 3974138492 47913 34304 Total Identified 2959957 2977271 2965920 24682762622351 2961117 2350318 Ex. 12 Ex. 10 Ex. 7 Ex. 16 Ex. 11 Ex. 17 Ex. 14Compound 375/200/1000 375/50/400 375/200/0 393/200/400 393/200/1000393/50/400 393/200/0 nC3 7269 5661 1236 6699 11669 7397 13908 iC4 1573912807 5387 17390 30066 16581 25595 nC4 48363 37939 20264 65885 11922863253 85782 iC5 90064 72666 55106 97547 156244 89843 121034 nC5 137002110901 88871 169827 286914 160735 194479 2MC5 115526 101998 85673 93272108420 84693 120618 3MC5 31677 26342 21791 28694 40690 26860 33718 nC6118146 100618 86522 129334 184005 126052 142388 MCyC5 37084 28565 2200347374 109121 46573 42081 Bz 7853 5046 1462 13841 32635 13298 5281 CyC67216 6215 4677 7782 16185 7796 6702 2MC6 15916 13707 11498 14158 1849313526 15983 2_3DMC5 10200 10045 8700 5872 5213 5221 8009 3MC6 3601232032 27592 26590 27008 24198 34632 c1_3DMCyC5 8745 6723 5653 1007720876 10166 10196 t1_3DMCyC5 7738 5919 4696 9288 20375 9410 8996t1_2DMCyC5 14871 12111 9093 14076 25486 13945 14016 nC7 88478 7988371376 84301 100677 83967 93851 MCyC6 21185 16612 13077 25416 52122 2694122527 ECyC5 9321 7481 5938 10785 20809 11141 10494 ctc1_2_4TMCyC5 54164342 3333 4973 8491 4876 5099 2_3_3TMC5 7701 6078 2721 8282 14107 84625820 Tol 16417 12571 7936 28390 81614 29969 15289 2MC7 64097 60547 5378143620 34674 40804 56500 4MC7 15831 14584 12924 9493 7239 8556 137413MC7+c1_3DMCyC6 16911 13585 10461 15740 25479 16746 15554 1_1DMCyC6 51424322 3549 4621 7524 4699 4489 t1_2DMCyC6 5651 4462 3155 6174 11333 65995786 nC8 72018 66566 61076 64505 72259 65997 72525 ECyC6 7000 5801 51098070 13555 8580 8331 IP9 30352 30154 29713 19489 10212 17783 285331_1_3TMCyC6 68812 65524 56646 46985 54500 46693 52535 EBz 5488 4430 30437868 22842 8534 5561 mXyl 45134 39173 27725 49533 89552 51545 390812_3DMC7 11746 12891 10928 17600 45058 18722 7594 3MC8 29983 28501 2500518399 12310 17096 24731 oXyl 13177 10318 6919 18339 46078 19916 12553nC9 79626 75732 70146 66190 62650 66077 78141 Cumene 7177 7111 6494 31785533 4313 5740 IP10 52477 52795 48281 27855 13405 24950 40164 1E3MBz13066 10278 7349 17552 40995 18896 13343 1E4MBz 20286 18035 13450 1987537841 20789 17314 1_3_5TMBz 40192 40307 29445 18792 37623 20422 233074MC9 27153 26459 23814 14129 7667 13118 20482 2MC9 13381 12026 1037812857 20387 13440 13690 3MC9 16690 19055 18064 4841 4289 16173 174581_2_4TMBz 34267 29903 21548 35775 64065 37666 29801 nC10 83296 8011875273 64751 56048 65746 80593 1_2_3TMBz 46723 43386 33967 37772 5976139883 38341 IP11 56917 58868 55471 26255 10528 23780 40754 1E3_5DMBz14220 13458 11588 10256 15328 10406 11157 Transdecaline 4627 4483 41614121 6263 4554 4332 5MC10 5910 7492 6898 2872 3790 3039 3820 2MC10 1585414055 11002 9448 20313 10543 7992 1E2_3DMBz 6445 6158 5036 5563 99426136 5707 nC11 62410 62409 59850 47595 37001 48821 61647 2_4DMC10 50845554 4997 3855 6788 4178 3670 Tetralin 3859 3862 3175 3551 6009 37033485 5MC11 9507 9301 8384 5169 3236 4919 7054 2MC11 6420 6212 5903 29397434 4831 5815 Naph 4045 5115 3471 1421 1335 3192 2146 nC12 47162 4592945161 32755 22642 32990 43792 IP13 36808 41276 38086 15279 7229 1396124531 HexylCyC6 6735 7805 7201 4063 10738 5909 5997 5MC12 6348 5805 57475449 8791 5702 5849 2MC12 6351 6715 6599 2403 2676 2476 3389 3MC12 76516800 6234 6489 9827 6687 7687 IP14 32862 38407 35926 10800 3824 934521461 2MNaph 11378 9218 8139 14756 30837 15289 11673 1MNaph 7379 68905949 7823 18060 8439 7329 nC13 49637 49013 49484 32927 21837 33203 46055IP15 34553 40638 39565 10930 6636 9395 20846 DMNaph 8910 7767 7155 999919469 10234 9255 nC14 46665 45946 49294 32498 20702 31519 441521_3&1_7DMNaph 11972 12768 13155 10766 20536 10877 9706 1_6DMNaph 3020328309 25197 27911 44268 28732 29189 IP16 35572 44986 44159 9430 18287803 20599 nC15 45224 45232 48033 29479 18676 29044 42973 nC16 4086541749 46405 26623 13755 25733 38544 IP18 24431 31626 32339 6256 23575234 13352 nC17 41281 42514 48243 23254 11287 24080 37090 Pristane 2736039776 41674 5703 4003 5775 13853 nC18 34948 36327 43770 20198 7554 1969331365 Phytane 14044 20341 21713 3351 2448 3020 7617 nC19 34009 3590645087 19100 8779 19319 30772 Total Identified 2521261 2381033 21271002065143 2800050 2051204 2447041

Analyses by liquid chromatography (LC) followed by gaschromatography/mass spectrometry (GC/MS) were performed on liquidsamples from Examples 6-20 (as indicated in the Examples). The LCprocedure separated the saturate and aromatic hydrocarbon fractions fromthe liquid or sediment sample produced in each Example. The saturate andaromatic fractions were then analyzed separately by GC/MS. Theprocedures for these analyses are described in the following sections.

LC Method

The LC procedure utilized silica gel as the separation medium and aselection of solvents in order to produce the saturate and aromaticextracts.

The LC procedure utilized the following laboratory equipment andchemicals:

-   -   1. Zymark Turbovap® Evaporator    -   2. Muffle furnace capable of operating at 400° C.    -   3. Centrifuge (1500 rpm capability such as Fisher Centrific®)    -   4. Glass chromatography columns (10 mm. ID×50 cm. length)    -   5. Other standard lab equipment as required—e.g., exhaust hood,        analytical balance, hot plate (40° C.) and refrigerator    -   6. Pentane (Fisher Optima grade or equivalent)    -   7. Hexane (Fisher Optima grade or equivalent)    -   8. Methylene chloride (Fisher Optima grade or equivalent)    -   9. Methanol (Fisher Optima grade or equivalent)    -   10. Silica gel (Fisher grade 923 @ 100-200 mesh)    -   11. Internal standards mixture as described below

The internal standards mixture was made in hexane with the compounds andconcentrations as shown Table 19:

TABLE 19 Compound Name Concentration (ng/μl) 5β Cholane 40.4 C13 Benzene40.8 d-Tetralin 42.0 2-Fluoro Biphenyl 31.2 d8 Naphthalene 30.0o-Terphenyl 21.2 d10 Fluoranthrene 20.3

The amount of the internal standards mixture to be added (as describedin the procedure to follow) was determined according to Table 20.

TABLE 20 Amount of Internal Std. Pentane Soluble (mg) Needed (μl) 65-5545 55-50 40 50-45 35 45-40 30 40-30 25 30-25 20 25-20 15 20-10 10 10-5 5

The internal standards were used to enable calculation of concentrationsand as known markers to facilitate compound identifications.

This LC method was used because it easily separates the crude oil orsediment extract sample into 4 compound classes including saturates,aromatics, NSO's (nitrogen, sulfur and oxygenate compounds), andasphaltenes.

The first separations in this LC procedure were the removal ofasphaltenes and the collection of the pentane soluble fraction asdescribed in Table 21:

TABLE 21 Step Action 1 Label sample vials or centrifuge tubes withsample number and type (PN, ASPH, SAT, ARO, and NSO). 2 Weigh all vialsand centrifuge tubes. 3 Weigh about 50 mgs of sample in a labeledcentrifuge tube. 4 Add 10 mls of pentane to centrifuge tube toprecipitate the asphaltenes. 5 Leave sample at room temperature for 4hours, and then centrifuge for 30 minutes at 1500 rpm (setting of 12 ona Fisher Centrific ® centrifuge). 6 Decant solvent in centrifuge tubeinto a 20-ml pre-weighed vial and blow dry with nitrogen at 40° C. Note:This is the pentane soluble fraction (PN). 7 Weigh the PN fraction. 8Transfer the residue in the centrifuge tube to a 20-ml pre-weighed vialusing methylene chloride and blow dry with nitrogen at 40° C. Note: Thisis the asphaltene fraction (ASPH).

Table 22 describes the liquid chromatographic separation procedure.

TABLE 22 Step Action 1 Activate the silica gel at 400° C. for 24 hours,then store in a desiccator. 2 Add the internal standards andapproximately 2 mls of pentane to the PN fraction and mix. Note: Amountof internal standards is determined from Table 20. 3 Pour 14 gms ofactivated silica gel to a liquid chromatography column and tap to pack.4 Add 5 mls of hexane to column as a pre-wet. As pre-wet enters gel, addcontents of vial from step 2 to column followed by 5 mls of additionalhexane and collect in a 50 ml evaporator tube (SAT fraction). Note: Ifthe saturate fraction develops some color, the column was overloaded.Repeat the LC separation using less sample. 5 Wash PN vial with two 10mls aliquots of hexane (20 mls total), adding to LC column as previousaddition enters the gel. 6 Switch to solvent of methylene chloride,continue adding 5 mls of solvent to the column 7 As the 5 mls ofmethylene chloride enters the gel, remove the evaporation tubecontaining the saturate fraction from the base of the column and replacewith another evaporation tube to collect the methylene chloride solublefraction (ARO fraction). 8 Add two 10 mls aliquots of methylene chloride(20 mls total) to the column in the same manner as the hexane additionsin step 5. 9 Switch to solvent of methylene chloride/methanol (50/50mix), continue adding 5 mls of solvent to column. 10 As the 5 mls ofmethylene chloride/methanol enters the gel, remove the evaporation tubecontaining the aromatic fraction from the base of the column and replacewith a 20 mls pre-weighed vial to collect the methylenechloride/methanol soluble fraction (NSO fraction). 11 Add two 10 mlsaliquots of methylene chloride/methanol to the column (20 mls total) inthe same manner as the hexane additions in step 5. Collect until columnis dry. 12 Using nitrogen, dry the evaporator tubes containing thehexane and methylene chloride fractions to a volume of 4 mls, using aTurbovap ® evaporator at 40° C. 13 Transfer the 4 mls to pre-weighedsample vials and dry to constant weight with nitrogen at 40° C. 14 Drythe methylene chloride/methanol vial to constant weight with nitrogen at40° C. 15 Weigh the ASPH, SAT, ARO, and NSO fractions. Note: The sum ofthe weights of the saturate, aromatic and NSO fractions should be equalor less than the weight of the PN soluble (SAT + ARO + NSO <= PN). Ifthe sum was greater after the fractions have been dried to constantweight, then the NSO fraction may have contained silica gel and a notewas placed in the laboratory journal. Such an occurrence is of noconsequence for the SAT and ARO fractions and their analyses, which arethe focus of this application.

Quality control for this LC procedure was maintained via the testing ofa standard oil sample (North Sea), which was run with the samples ofinterest. Percentages of the SAT, ARO,

NSO and ASPH fractions (based on the whole sample) were calculated andQC charts maintained.

GC/MS Method: The GC/MS was performed using an HP 6890 gas chromatograph(GC) connected to an HP 5973 MSD mass spectrometer (MS) equipped with amass selective detector. In addition, an autosampler (equipped with a 10μl syringe) and Agilent ChemStation software (version G1710DA forMicrosoft XP®) were used. The mass spectrometric method used was SIM(selected ion monitoring) for analysis of the saturated and aromaticcomponents, which were collected as described in the previous section.

Materials used:

-   -   Hexane (Fisher Optima grade or equivalent)    -   GC column—J&W DB-5 fused silica (Agilent)    -   UHP Helium (Air Liquide)    -   Methylene chloride (Fisher Optima grade or equivalent)

Sample Preparation: Each liquid sample to be analyzed was transferred toa sample vial suitable for use in the GC/MS equipment, the concentrationadjusted to 25 μg/μl by the addition of hexane. The vial was sealed andplaced in the autosampler.

GC conditions: The GC employed a J&W DB-5 fused silica capillary column,which was 30 meters in length, 0.25 mm inner diameter and had 0.25 μmfilm thickness. GC settings for the saturate fractions were those shownin Table 23.

TABLE 23 Parameter Setting Injection mode Split Inlet Temp 310° C.Pressure 9 psi Split ratio 5:1 Total flow 8.0 mL/min Temperature program75-200 @ 5° C./min - 315 @ 3° C./min (hold for 15 mins)

GC settings for the aromatic fractions were as indicated in Table 24.

TABLE 24 Parameter Setting Injection mode Split with split ratio = 5:1Inlet Temp 310° C. Pressure 9.38 psi Total flow 7.0 mL/min Temperatureprogram 80-200 @ 5° C./min - 315 @ 6° C./min, hold for 20 mins

MS conditions: Methylene chloride was used to clean components of the MSas needed. MS source and quad temperatures were set as shown in Table25.

TABLE 25 Parameter Setting MS Quad 150° C., maximum 200° C. MS Source230° C., maximum 250° C.

MS SIM parameters for the saturate and aromatic fractions were set asshown in Table 26.

TABLE 26 Parameter Setting Solvent delay 20 min Acquisition mode SIMMonitoring ions See list below Dwell time 100 ms

Additionally the following list of saturates and aromatics was used tofacilitate compound identification.

Saturates:

m/z 123: terpenoidsm/z 125: beta-carotanem/z 177: C29 terpanes, 25-norhopanesm/z 183: isoprenoidsm/z 191: terpanesm/z 205: methyl hopanesm/z 217: steranesm/z 218: abb-steranesm/z 231: steranesm/z 259: diasteranes

Aromatics:

Naphthalenes: m/z 128 (C0), m/z 142 (C1), m/z 156 (C2), m/z 170 (C3),m/z 184 (C4 & dibenzothiophene)

Phenanthrenes: m/z 178 (C0), m/z 192 (C1), m/z 206 (C2), m/z 220 (C3)

Dibenzothiophenes: m/z 184 (C0 & C4 naphthalenes), m/z 198 (C1), m/z 212(C2)Aromatic Steroids: m/z 231 (and C1 benzocarbozoles), m/z 245 (and C2benzocarbozoles), m/z 253

Chrysenes: m/z 228 (C0), m/z 242 (C1), m/z 256 (C2), m/z 270 (C3)Carbozoles: m/z 167 (C0), m/z 181 (C1), m/z 195 (C2)

Benzocarbozoles: m/z 217 (C0), m/z 231 (C1 and triaromatic steroids),m/z 245 (C2 and triaromatic dinosteroids)

Benzohopanes: m/z 191 Biphenyls: m/z 154 (C0), m/z 168 (C1), m/z 182(C2) Fluorenes: m/z 166 (C0), m/z 180 (C1), m/z 194 (C2)

MS instrument settings were adjusted to achieve the detection limitslisted in Table 27 over a range of mass values:

TABLE 27 Tune target Limit Mass 50 1 Mass 131 40 Mass 219 60 Mass 414 10Mass 502 5 Peak width 0.55 Abundance 400,000

Analysis and reporting of the data: Peak assignments in the GC/MSchromatograms were made utilizing a known oil reference standard (NorthSea, Jurassic sourced oil from the Kimmeridge) and an internal standard(5(3-Cholane for the saturates and o-Terphenyl, C13 Benzene for thearomatics). The geochemical patterns were confirmed by both retentiontime and diagnostic mass to charge ratios since most of thesegeochemical compounds are not commercially available. In addition, usewas made of spectral patterns of typical compounds found in oil samplesand studied extensively in the literature such as those described in thefollowing reference: The Biomarker Guide, by Kenneth E. Peters and J.Michael Moldowan, Prentice Hall Publishing, 1993.

The spectral quality and reproducibility of the GC/MS data weremaintained by frequent runs of a previously known crude oil that wasseparated into fractions by liquid chromatography (as described in thismethod). Ratios from this standard (i.e., the North Sea oil mentionedabove) were used for quality control purposes. A mass calibrant(perfluorotributylamine) was used for the MS prior to instrumentalanalysis. These data were used to ensure accurate peak positions and toensure reproducibility of peak area ratios through time.

The concentrations of molecular species found in the chromatogramsgenerated by the GC/MS analysis were determined by manually measuringpeak heights for each compound of interest. The baseline for eachmeasurement was taken as the mean baseline for the peak extrapolatedfrom the low background to the high background. When nearby peaks causedthe immediately adjacent background to be too high the background wasestimated by linear fit to average background for compounds elutingwithin 2 minutes of the molecule of interest. For each sample, all peakheights were measured in the same chromatogram or scaled to a singlechromatogram in instances where very large peak heights introducedgraphical error in measuring smaller peaks.

The above-described processes may be of merit in connection with therecovery of hydrocarbons in the Piceance Basin of Colorado. Some haveestimated that in some oil shale deposits of the Western United States,up to 1 million barrels of oil may be recoverable per surface acre. Onestudy has estimated the oil shale resource within the nahcolite-bearingportions of the oil shale formations of the Piceance Basin to be 400billion barrels of shale oil in place. Overall, up to 1 trillion barrelsof shale oil may exist in the Piceance Basin alone.

Certain features of the present invention are described in terms of aset of numerical upper limits and a set of numerical lower limits. Itshould be appreciated that ranges formed by any combination of theselimits are within the scope of the invention unless otherwise indicated.Although some of the dependent claims have single dependencies inaccordance with U.S. practice, each of the features in any of suchdependent claims can be combined with each of the features of one ormore of the other dependent claims dependent upon the same independentclaim or claims.

While it will be apparent that the invention herein described is wellcalculated to achieve the benefits and advantages set forth above, itwill be appreciated that the invention is susceptible to modification,variation and change without departing from the spirit thereof.

1. An in situ method of producing hydrocarbon fluids from anorganic-rich rock formation, comprising: a) heating in situ a section ofan organic-rich rock formation containing formation hydrocarbons, thesection of the organic-rich rock formation having a lithostatic stress;b) pyrolyzing at least a portion of the formation hydrocarbons therebyforming a hydrocarbon fluid; and c) producing the hydrocarbon fluid fromthe organic-rich rock formation, the produced hydrocarbon fluidcomprising a condensable hydrocarbon portion, the condensablehydrocarbon portion having: i) one or more of a n-C6 to benzene weightratio less than 35.0, a n-C7 to toluene weight ratio less than 7.0, an-C8 to ethylbenzene weight ratio less than 16.0, a n-C8 to ortho-xyleneweight ratio less than 7.0, a n-C8 to meta-xylene weight ratio less than1.9, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 8.2, an-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.4, a n-C9 to1,2,4-trimethylbenzene weight ratio less than 2.7, a n-C10 to1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, a n-C10 totetralin weight ratio less than 25.0, a n-C12 to 2-methylnaphthaleneweight ratio less than 4.9, and a n-C12 to 1-methylnaphthalene weightratio less than 6.9; ii) one or more of a n-C9 to IP-9 weight ratiogreater than 2.4, a n-C10 to IP-10 weight ratio greater than 1.4, an-C11 to IP-11 weight ratio greater than 1.0, a n-C13 to IP-13 weightratio greater than 1.1, a n-C14 to IP-14 weight ratio greater than 1.1,a n-C15 to IP-15 weight ratio greater than 1.0, a n-C16 to IP-16 weightratio greater than 0.8, a n-C18 to IP-18 weight ratio greater than 1.0,and a n-C19 to pristane weight ratio greater than 1.6; iii) one or moreof a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 13.1,a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 14.9, an-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 7.0, an-C7 to methyl cyclohexane weight ratio less than 5.2, a n-C7 to ethylcyclopentane weight ratio less than 11.3, a n-C8 to 1,1-dimethylcyclohexane weight ratio less than 16.0, a n-C8 to trans 1,2-dimethylcyclohexane weight ratio less than 17.5, and a n-C8 to ethyl cyclohexaneweight ratio less than 12.3; iv) one or more of a total C10 to total C20weight ratio greater than 2.8, a total C11 to total C20 weight ratiogreater than 2.3, a total C12 to total C20 weight ratio greater than2.3, a total C13 to total C20 weight ratio greater than 2.9, a total C14to total C20 weight ratio greater than 2.2, a total C15 to total C20weight ratio greater than 2.2, and a total C16 to total C20 weight ratiogreater than 1.6; v) one or more of a total C10 to total C25 weightratio greater than 7.5, a total C11 to total C25 weight ratio greaterthan 6.5, a total C12 to total C25 weight ratio greater than 6.5, atotal C13 to total C25 weight ratio greater than 8.0, a total C14 tototal C25 weight ratio greater than 6.0, a total C15 to total C25 weightratio greater than 6.0, a total C16 to total C25 weight ratio greaterthan 4.5, a total C17 to total C25 weight ratio greater than 4.8, and atotal C18 to total C25 weight ratio greater than 4.5; vi) one or more ofa total C7 to total C29 weight ratio greater than 3.5, a total C8 tototal C29 weight ratio greater than 9.0, a total C9 to total C29 weightratio greater than 12.0, a total C10 to total C29 weight ratio greaterthan 15.0, a total C11 to total C29 weight ratio greater than 13.0, atotal C12 to total C29 weight ratio greater than 12.5, a total C13 tototal C29 weight ratio greater than 16.0, a total C14 to total C29weight ratio greater than 12.0, a total C15 to total C29 weight ratiogreater than 12.0, a total C16 to total C29 weight ratio greater than9.0, a total C17 to total C29 weight ratio greater than 10.0, a totalC18 to total C29 weight ratio greater than 8.8, a total C19 to total C29weight ratio greater than 7.0, a total C20 to total C29 weight ratiogreater than 6.0, a total C21 to total C29 weight ratio greater than5.5, and a total C22 to total C29 weight ratio greater than 4.2; vii)one or more of a normal-C7 to normal-C20 weight ratio greater than 0.9,a normal-C8 to normal-C20 weight ratio greater than 2.0, a normal-C9 tonormal-C20 weight ratio greater than 1.9, a normal-C10 to normal-C20weight ratio greater than 2.2, a normal-C11 to normal-C20 weight ratiogreater than 1.9, a normal-C12 to normal-C20 weight ratio greater than1.9, a normal-C13 to normal-C20 weight ratio greater than 2.3, anormal-C14 to normal-C20 weight ratio greater than 1.8, a normal-C15 tonormal-C20 weight ratio greater than 1.8, and normal-C16 to normal-C20weight ratio greater than 1.3; viii) one or more of a normal-C10 tonormal-C25 weight ratio greater than 4.4, a normal-C11 to normal-C25weight ratio greater than 3.8, a normal-C12 to normal-C25 weight ratiogreater than 3.7, a normal-C13 to normal-C25 weight ratio greater than4.7, a normal-C14 to normal-C25 weight ratio greater than 3.7, anormal-C15 to normal-C25 weight ratio greater than 3.7, a normal-C16 tonormal-C25 weight ratio greater than 2.5, a normal-C17 to normal-C25weight ratio greater than 3.0, and a normal-C18 to normal-C25 weightratio greater than 3.4; ix) one or more of a normal-C7 to normal-C29weight ratio greater than 18.0, a normal-C8 to normal-C29 weight ratiogreater than 16.0, a normal-C9 to normal-C29 weight ratio greater than14.0, a normal-C10 to normal-C29 weight ratio greater than 14.0, anormal-C11 to normal-C29 weight ratio greater than 13.0, a normal-C12 tonormal-C29 weight ratio greater than 11.0, a normal-C13 to normal-C29weight ratio greater than 10.0, a normal-C14 to normal-C29 weight ratiogreater than 9.0, a normal-C15 to normal-C29 weight ratio greater than8.0, a normal-C16 to normal-C29 weight ratio greater than 8.0, anormal-C17 to normal-C29 weight ratio greater than 6.0, a normal-C18 tonormal-C29 weight ratio greater than 6.0, a normal-C19 to normal-C29weight ratio greater than 5.0, a normal-C20 to normal-C29 weight ratiogreater than 4.0, a normal-C21 to normal-C29 weight ratio greater than3.6, and a normal-C22 to normal-C29 weight ratio greater than 2.8; or x)one or more of a normal-C10 to total C10 weight ratio less than 0.31, anormal-C11 to total C11 weight ratio less than 0.32, a normal-C12 tototal C12 weight ratio less than 0.29, a normal-C13 to total C13 weightratio less than 0.28, a normal-C14 to total C14 weight ratio less than0.31, a normal-C15 to total C15 weight ratio less than 0.27, anormal-C16 to total C16 weight ratio less than 0.31, a normal-C17 tototal C17 weight ratio less than 0.31, a normal-C18 to total C18 weightratio less than 0.37, normal-C19 to total C19 weight ratio less than0.37, a normal-C20 to total C20 weight ratio less than 0.37, anormal-C21 to total C21 weight ratio less than 0.37, a normal-C22 tototal C22 weight ratio less than 0.38, normal-C23 to total C23 weightratio less than 0.43, a normal-C24 to total C24 weight ratio less than0.48, and a normal-C25 to total C25 weight ratio less than 0.53.
 2. Themethod of claim 1, wherein the organic-rich rock formation is an oilshale formation.
 3. The method of claim 1 further comprising the step ofselecting a pillar geometry to alter the lithostatic stress of thesection of the organic-rich rock formation.
 4. The method of claim 3wherein the altered lithostatic stress is greater than 200 psi.
 5. Themethod of claim 1 further comprising the step of selecting a pillarlocation to alter the lithostatic stress of the section of theorganic-rich rock formation.
 6. The method of claim 5 wherein thealtered lithostatic stress is greater than 200 psi.
 7. The method ofclaim 1 further comprising the step of selecting a heating and pyrolysisformation region thickness to alter the lithostatic stress of thesection of the organic-rich rock formation.
 8. The method of claim 7wherein the altered lithostatic stress is greater than 200 psi.
 9. Themethod of claim 1 further comprising the step of selecting a heatingsequence to alter the lithostatic stress of the section of theorganic-rich rock formation.
 10. The method of claim 9 wherein thealtered lithostatic stress is greater than 200 psi.